CN103965388A

CN103965388A - Novel polymer compositions and methods of making and using same

Info

Publication number: CN103965388A
Application number: CN201410043326.2A
Authority: CN
Inventors: M·L·赫拉温卡; 杨清; W·B·蟠龙; P·J·戴斯劳瑞斯
Original assignee: Chevron Phillips Chemical Co LLC
Current assignee: Chevron Phillips Chemical Co LLC; Chevron Phillips Chemical Co LP
Priority date: 2013-01-29
Filing date: 2014-01-29
Publication date: 2014-08-06
Also published as: BR112015018136B1; EP2951237B1; MX361988B; US20150210786A1; SG11201505955PA; CA2899689A1; WO2014120540A1; US9394385B2; US20160168290A1; ES2609782T3; US9637573B2; US20140213747A1; MX2015009775A; EP2951237A1; CA2899689C; US9034991B2

Abstract

A polymer reactor-blend comprising at least a first component having a polydispersity index of greater than about 20 and is present in an amount of from about 1 wt. % to about 99 wt. % based on the total weight of the polymer and a second component having a polydispersity index of less than about 20 and is present in an amount of from about 1 wt. % to about 99 wt. % based on the total weight of the polymer wherein a molecular weight distribution of the second component lies within a molecular weight distribution of the first component.

Description

Novel polymeric compositions and methods for making and using same thereof

The cross reference of related application

The application's theme relates to the U.S. Patent application the 13/753rd that the name of meanwhile submitting to is called " novel catalyst composition and methods for making and using same thereof ", No. 289 [attorney docket 211492US00 (4081-20000)], its full content is introduced into herein by reference, for whole objects.

Background of invention

The disclosure relates generally to catalyst system and polymer composition.Particularly, the disclosure relates to the novel catalyst composition for the production of multimodal polymer resin.

Invention field

Polyolefine is plastic material, because its feature is as rigidity, ductility, barrier, temperature tolerance, optical characteristics, operability with combine cheaply and can be used for preparing multiple value product.Particularly, polyethylene (PE) is one of polymkeric substance of the maximum that consumes in the world.It is with respect to other polymkeric substance and can material selection if glass or metal carrying are for high performance multifunctional polymer.

Multimodal PE resin provides the possibility of widespread use, because these resins can combine desirable physical properties and processing characteristics.There is lasting demand for the improved catalyst system for the production of polymer composition.

Summary of the invention

Herein disclosed is the reactor blend of polymkeric substance, it at least comprises the first component, the polydispersity index of described the first component be greater than approximately 20 and the amount that exists be about 1wt.% to about 99wt.% based on total polymer weight; And second component, the polydispersity index of described second component be less than approximately 20 and the amount that exists be about 1wt.% to about 99wt.% based on total polymer weight, wherein in the molecular weight distribution of the molecular weight distribution of second component in the first component.

Also disclose pipe-making method herein, comprised vinyl monomer is contacted with catalyst composition with 1-hexene, this catalyst composition comprises (i) imines (two) phenates compound, and it has structure XIV

Wherein M is the 3rd family's to the 12 group 4 transition metals or lanthanon; R2 and R3 can be hydrogen, halogen, alkyl or substituted hydrocarbon radical independently of one another; (ii) metallocene, under the condition that is suitable for forming polymkeric substance and Et ₂o is optional; Reclaim polymkeric substance; With polymkeric substance is made to pipe, wherein to be about 1E+05Pa-s be less than approximately 600% to about 1E+10Pa-s and natural draw ratio (tensile natural draw ratio) to the zero-shear viscosity of polymkeric substance, and wherein the PENT value of pipe is greater than approximately 800 hours, as utilized 3.8MPa stress determination according to ASTM F1473.

The reactor blend of polymkeric substance is also disclosed herein, its polydispersity index be greater than approximately 15 and short-chain branched distribution maximum value be present between about 30kDa and the weight-average molecular weight of 1000kDa.

Brief description of the drawings

Fig. 1 is representative tensile stress-strain curve.

Fig. 2 is the gel permeation chromatography figure from the sample of embodiment.

Fig. 3 is the drawing as the function of frequency from the dynamic fusion viscosity of the sample of embodiment.

Figure 4 and 5 are the drawing from the short-chain branched distribution of the sample of embodiment.

Embodiment

Herein disclosed is new catalyst and polymer composition and methods for making and using same thereof.In embodiment, catalyst composition comprises the metal salt complex of imines phenolic compound and the mixture of at least one containing metal cyclopentadinyl compound, and is named as in this article CATCOMP.CATCOMPs can be used for producing the multimodal polymer composition that presents desirable performance and processing characteristics.These aspects of the present disclosure are further described in this article.

For limiting more clearly term used herein, provide to give a definition.Except as otherwise noted, be applicable to the disclosure to give a definition.If a term is used for the disclosure but is not specifically limited in this article, applicable from IUPAC Compendium of Chemical Terminology, 2 ^ndthe definition of Ed (1997), as long as this definition does not conflict with any other open or definition of application herein or cause the applied any opinion of this definition indefinite or be false.In the situation of any definition that any file being incorporated to by reference herein provides or application and definition provided herein or application collision, definition provided herein or application occupy leading.

Biao Zhongge family element utilizes Chemical and Engineering News, and the numbering plan shown in 63 (5), 27,1985 disclosed periodic table of elements versions represents.In some instances, gang's element can represent with the common name of this family of name; For example, alkaline-earth metal (or basic metal)---the 1st family's element, alkaline-earth metal (or basic metal)---the 2nd family's element, transition metal---3-12 family element, and halogen---the 17th family's element.

How chemistry " group " is described derived from reference or " parent " compound in form according to group, for example, thereby by removing from parent compound the hydrogen atom quantity that generates this group in form, even if this group is not to synthesize in this way on word.These groups can be used as substituting group or coordination or are bonded to atoms metal.As an example, " alkyl " in form can be derivative by removing a hydrogen atom from alkane, and " alkylidene group " in form can be derivative by removing two hydrogen atoms from alkane.In addition, available more general term is included in form by remove the derivative multiple group of any amount (" one or more ") hydrogen atom from parent compound, it can be described to " alkane group " in this example, comprises " alkyl ", " alkylidene group " and by the required material of removing three or more hydrogen atoms from alkane of situation.From beginning to end, substituting group, part or other chemical part can form the concrete disclosure of " group " implied this group as described in follow the known rule of chemical structure and bonding while applying." pass through ... derivative " when group is described as, " derived from ", " passing through ... form " or " by ... form " time, such term uses in form meaning, be not intended to reflect any concrete synthetic method or program, unless illustrated in addition or the other requirement of context.

Term " replacement " is when describing group, and for example, in the time relating to the replacement analogue of concrete group, intention is described in any non-hydrogen partial that in form substitutes the hydrogen in this group, and is intended that nonrestrictive.One or more groups also can be called as " unsubstituted " or equivalent terms in this article as " non-substituted ", and it means non-hydrogen partial wherein and substitute the original group of the hydrogen in this group." replacement " is intended that nonrestrictive, and comprises inorganic substituting group or organic substituent.

Unless illustrated in addition, any carbon-containing group that amount of carbon atom is not illustrated can have any range between 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29 or 30 carbon atom or these values or the combination of scope according to suitable Practical in Chemistry.For example, unless illustrated in addition, carbon-containing group can have 1 to 30 carbon atom, 1 to 25 carbon atom, 1 to 20 carbon atom, 1 to 15 carbon atom, 1 to 10 carbon atom or 1 to 5 carbon atom etc. arbitrarily.In addition, other mark or restriction term can be used for representing to exist or do not exist concrete substituting group, concrete regional chemistry and/or stereochemistry or having or do not exist branch's foundation structure or skeleton.

Definition that term " organic radical (organyl group) " specifies according to IUPAC is in this article used: no matter sense type has the organic substituent of a free valency at carbon atom place.Similarly, " sub-organic radical (organylenegroup) " means: no matter sense type, by remove the derivative organic group of two hydrogen atoms (remove two hydrogen atoms from a carbon atom, or respectively remove a hydrogen atom from two different carbon atoms) from organic compound." organic group (organic group) " means the summary group forming by remove one or more hydrogen atoms from the carbon atom of organic compound.Therefore, " organic radical ", " sub-organic radical " and " organic group " can comprise organo-functional group (one or more) and/or the atom (one or more) of non-carbon and hydrogen,, organic group can comprise de-carbon and hydrogen functional group and/or atom in addition.For example, the limiting examples of the atom of non-carbon and hydrogen comprises halogen, oxygen, nitrogen, phosphorus etc.The limiting examples of functional group comprises ether, aldehyde, ketone, ester, sulfide, amine, phosphine etc.On the one hand; the hydrogen atom (one or more) that formation " organic radical ", " sub-organic radical " or " organic group " are removed can be connected in the carbon atom that belongs to functional group; for example, acyl group (C (O) R), formyl radical (C (O) H), carboxyl (C (O) OH),-oxyl carbonyl (C (O) OR), cyano group (C=N), formamyl (C (O) NH ₂), M alkyl formamyl (C (O) NHR) or N, N'-dialkyl formamyl (C (O) NR ₂) etc.On the other hand, the hydrogen atom (one or more) that formation " organic radical ", " sub-organic radical " or " organic group " are removed can be connected in the carbon atom that does not belong to and be away from functional group, for example, and-CH ₂c (O) CH ₃,-CH ₂nR ₂deng." organic radical ", " sub-organic radical " or " organic group " can be aliphatic, include ring or acyclic, can be maybe aromatic.Organic radical ", " sub-organic radical " and " organic group " also comprise containing heteroatomic ring, containing heteroatomic loop systems, heteroaromatic ring and heteroaromatic loop systems." organic radical ", " sub-organic radical " and " organic group " can be straight or brancheds, unless illustrated in addition.Finally, notice that " organic radical ", " sub-organic radical " or " organic group " definition comprise respectively " alkyl ", " alkylene ", " hydrocarbyl group " and comprise that respectively " alkyl ", " alkylidene group " and " alkane group " are as member.

Whenever term " alkane ", use in the present specification and claims, all means saturated hydrocarbon compound.Other mark can be used for representing existing in alkane concrete group (for example, halogenation alkane represents to exist one or more halogen atoms to substitute the hydrogen atom of equivalent amount in alkane).The definition that term " alkyl " specifies according to IUPAC is in this article used: by removing from alkane the monoradical that a hydrogen atom forms.Similarly, " alkylidene group " means the group forming by remove two hydrogen atoms (remove two hydrogen atoms from a carbon atom, or remove a hydrogen atom from two different carbon atoms) from alkane." alkane group " is to summarize term, means the group forming by remove one or more hydrogen atoms (by the needs of concrete group) from alkane." alkyl ", " alkylidene group " and " alkane group " can be acyclic or have cyclic group, and/or can be straight or branched, unless illustrated in addition.Primary, secondary and tertiary alkyl derives by removing a hydrogen atom from primary, secondary, the tertiary carbon atom of alkane respectively.Alkyl can be removed a hydrogen atom by the end carbon atom from straight-chain paraffin and derive.Radicals R CH ₂(R ≠ H), R ₂cH (R ≠ H) and R ₃c (R ≠ H) is respectively primary, secondary and tertiary alkyl.

" halogen root (halide) " has its common implication; Therefore, the example of halogen root comprises fluorine root, chlorine root, bromine root and iodine root.

In the disclosure, be as the criterion with the standard rule of organic nomenclature.For example, in the time relating to the compound of replacement or group, with reference to substitute mode represent the group (one or more) of instruction be positioned at indicating positions and all other non-indicating positions be hydrogen.For example, represent to exist non-hydrogen substituting group to be positioned at 4 and hydrogen about 4-substituted-phenyl and be positioned at 2,3,5 and 6.As another example, replace naphthalene-2-basis representation about 3-and exist non-hydrogen substituting group to be positioned at 3 and hydrogen to be positioned at 1,4,5,6,7 and 8.Also there is substituent compound or group comprises utilization or some other optional language relate to about the position beyond the indicating positions.For example, mean to there is non-hydrogen atom and at 2,3,5 and 6 groups with hydrogen or any non-hydrogen group at 4 about comprising substituent phenyl at 4.

Embodiment disclosed herein can provide limit by term "or", be suitable for meeting the material that embodiment specific features is enumerated.For example, the specific features of this theme can disclose as follows: feature X can be A, B or C.Also consider, the statement of each feature also available phrase is expressed as enumerating of option, and making statement " feature X is A, B alternatively, or C alternatively " is also embodiment of the present disclosure, and no matter whether this statement is clearly recorded.

In embodiment, CATCOMP comprises imines phenolic compound, it is characterized in that structure I:

Wherein O and N represent respectively oxygen and nitrogen, and Q represents donor groups.R, R ²and R ³in one or more can be identical or different separately, and can be selected from embodiment as herein described.R can be halogen, alkyl or substituted hydrocarbon radical.In embodiment, R is not hydrogen.R ²and R ³can be hydrogen, halogen, alkyl or substituted hydrocarbon radical independently of one another.These substituting groups are described in more detail in this article.

Reference configuration I, generally, R, R ²and R ³can be alkyl independently of one another.In embodiment, R, R ²and R ³can be C independently of one another ₁to C ₃₀alkyl; C ₁to C ₂₀alkyl; C ₁to C ₁₅alkyl; C ₁to C ₁₀alkyl; Or C ₁to C ₅alkyl.In other embodiments, R, R ²and R ³can be C independently of one another ₃to C ₃₀aromatic group; C ₃to C ₂₀aromatic group; C ₃to C ₁₅aromatic group; Or C ₃to C ₁₀aromatic group.

On the one hand, R, R ²and R ³can be C independently of one another ₁to C ₃₀alkyl, C ₄to C ₃₀cycloalkyl, C ₄to C ₃₀substituted cycloalkyl, C ₃to C ₃₀aliphatic heterocyclic group, C ₃to C ₃₀replace aliphatic heterocyclic group, C ₆to C ₃₀aryl, C ₆to C ₃₀substituted aryl, C ₇to C ₃₀aralkyl, C ₇to C ₃₀substituted aralkyl, C ₃to C ₃₀heteroaryl or C ₃to C ₃₀substituted heteroaryl.In embodiment, R, R ²and R ³can be C independently of one another ₁to C ₁₅alkyl, C ₄to C ₂₀cycloalkyl, C ₄to C ₂₀substituted cycloalkyl, C ₃to C ₂₀aliphatic heterocyclic group, C ₃to C ₂₀replace aliphatic heterocyclic group, C ₆to C ₂₀aryl, C ₆to C ₂₀substituted aryl, C ₇to C ₂₀aralkyl, C ₇to C ₂₀substituted aralkyl, C ₃to C ₂₀heteroaryl or C ₃to C ₂₀substituted heteroaryl.In other embodiments, R, R ²and R ³can be C independently of one another ₁to C ₁₀alkyl, C ₄to C ₁₅cycloalkyl, C ₄to C ₁₅substituted cycloalkyl, C ₃to C ₁₅aliphatic heterocyclic group, C ₃to C ₁₅replace aliphatic heterocyclic group, C ₆to C ₁₅aryl, C ₆to C ₁₅substituted aryl, C ₇to C ₁₅aralkyl, C ₇to C ₁₅substituted aralkyl, C ₃to C ₁₅heteroaryl or C ₃to C ₁₅substituted heteroaryl.In further embodiment, R, R ²and R ³can be C independently of one another ₁to C ₅alkyl.

In embodiment, R, R ²and R ³can be methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl or nonadecyl independently of one another.In some embodiments, can be used as R, R ²and R ³alkyl can be substituted independently of one another.Each substituting group of substituted alkyl can be halogen or-oxyl independently; Alternatively, halogen; Or alternatively,-oxyl.Can be used as substituent halogen and-oxyl and be disclosed in this article independently, and can be used as R, R for further describing ad lib ²and/or R ³substituted alkyl.

In embodiment, R, R ²and R ³can be cyclobutyl, substituted ring butyl, cyclopentyl, substituted ring amyl group, cyclohexyl, substituted cyclohexyl, suberyl, substituted ring heptyl, ring octyl group or substituted ring octyl group independently of one another.In some embodiments, R, R ²and R ³can be cyclopentyl, substituted ring amyl group, cyclohexyl or substituted cyclohexyl independently of one another.

In embodiment, can be used as R, R ²and R ³each substituting group of substituted cycloalkyl (summarize or concrete) can be halogen, alkyl or-oxyl independently of one another.In some embodiments, can be used as R, R ²and R ³each substituting group of substituted cycloalkyl (summarize or concrete) can be halogen, alkyl or alkoxyl group independently of one another.Can be used as substituent halogen, alkyl,-oxyl, alkyl and alkoxyl group in this article by open independently, and can be used as R, R for further describing ad lib ²and/or R ³the substituting group (summarize or concrete) of substituted cycloalkyl.

On the one hand, R, R ²and R ³can there is independently of one another structure I I:

Wherein do not specify price (*) to represent substituting group (, R, R ²or R ³) be connected in the point at the transition metal salt complex place of structure I.Generally, R ^21c, R ^23c, R ^24cand R ^25ccan be hydrogen or non-hydrogen substituting group independently, and n can be 1 to 5 integer.

At R, R ²and R ³there is in the embodiment of structure I I R ^21c, R ^23c, R ^24cand R ^25ccan be hydrogen, and R ^22cit can be any non-hydrogen substituting group disclosed herein; Or alternatively, R ^21c, R ^23cand R ^25ccan be hydrogen, and R ^22cand R ^24ccan be any non-hydrogen substituting group disclosed herein independently.In embodiment, n can be 1 to 4 integer; Or alternatively, 2 to 4.In other embodiments, n can be 2 or 3; Alternatively, 2; Or alternatively, 3.

In embodiment, R ^21c, R ^22c, R ^23c, R ^24cand R ^25ccan be hydrogen, halogen, alkyl or-oxyl independently; Alternatively, hydrogen, halogen or alkyl.In some embodiments, R ^21c, R ^22c, R ^23c, R ^24cand R ^25ccan be hydrogen, halogen, alkyl or alkoxyl group independently.Can be used as substituent halogen, alkyl,-oxyl, alkyl and alkoxyl group in this article by open independently, and can there is ad lib R, the R of structure I I for further describing ²or R ³group.

In embodiment, R, R ²and R ³can be phenyl or substituted-phenyl independently of one another.In embodiment, substituted-phenyl can be 2-substituted-phenyl, 3-substituted-phenyl, 4-substituted-phenyl, 2,4-di-substituted-phenyl, 2,6-di-substituted-phenyl, 3,5-di-substituted-phenyl or 2,4,6-tri-substituted phenyl.

In embodiment, each substituting group of substituted-phenyl can be halogen, alkyl or-oxyl independently.In some embodiments, each substituting group of substituted-phenyl can be halogen, alkyl or alkoxyl group independently.Can be used as substituent halogen, alkyl,-oxyl, alkyl and alkoxyl group in this article by open independently, and can be ad lib for further describing the substituting group of substituted-phenyl.

On the one hand, R, R ²and R ³can there is independently of one another structure III:

Wherein do not specify price (*) to represent substituting group (, R, R ²or R ³) be connected in the point at the transition metal salt complex place of structure I.Generally, R ²², R ²³, R ²⁴, R ²⁵and R ²⁶can be hydrogen or non-hydrogen substituting group independently.At R, R ²or R ³there is in the embodiment of structure III R ²², R ²³, R ²⁴, R ²⁵and R ²⁶can be hydrogen; R ²³, R ²⁴, R ²⁵and R ²⁶can be hydrogen, and R ²²it can be non-hydrogen substituting group; R ²², R ²⁴, R ²⁵and R ²⁶can be hydrogen, and R ²³it can be non-hydrogen substituting group; R ²², R ²³, R ²⁵and R ²⁶can be hydrogen, and R ²⁴it can be non-hydrogen substituting group; R ²³, R ²⁵and R ²⁶can be hydrogen, and R ²²and R ²⁴it can be non-hydrogen substituting group; R ²³, R ²⁴and R ²⁵can be hydrogen, and R ²²and R ²⁶it can be non-hydrogen substituting group; R ²², R ²⁴and R ²⁶can be hydrogen, and R ²³and R ²⁵it can be non-hydrogen substituting group; Or R ²³and R ²⁵can be hydrogen, and R ²², R ²⁴and R ²⁶it can be non-hydrogen substituting group.At R, R ²or R ³there is in some embodiments of structure III R ²³, R ²⁴, R ²⁵and R ²⁶can be hydrogen, and R ²²it can be non-hydrogen substituting group; R ²², R ²³, R ²⁵and R ²⁶can be hydrogen, and R ²⁴it can be non-hydrogen substituting group; R ²³, R ²⁵and R ²⁶can be hydrogen, and R ²²and R ²⁴it can be non-hydrogen substituting group; R ²³, R ²⁴and R ²⁵can be hydrogen, and R ²²and R ²⁶it can be non-hydrogen substituting group; Or R ²³and R ²⁵can be hydrogen, and R ²², R ²⁴and R ²⁶it can be non-hydrogen substituting group; Alternatively, R ²³, R ²⁴, R ²⁵and R ²⁶can be hydrogen, and R ²²it can be non-hydrogen substituting group; R ²², R ²³, R ²⁵and R ²⁶can be hydrogen, and R ²⁴it can be non-hydrogen substituting group; R ²³, R ²⁵and R ²⁶can be hydrogen, and R ²²and R ²⁴it can be non-hydrogen substituting group; Or R ²³, R ²⁴and R ²⁵can be hydrogen, and R ²²and R ²⁶it can be non-hydrogen substituting group; Alternatively, R ²², R ²⁴, R ²⁵and R ²⁶can be hydrogen, and R ²³it can be non-hydrogen substituting group; Or R ²², R ²⁴and R ²⁶can be hydrogen, and R ²³and R ²⁵it can be non-hydrogen substituting group; Alternatively, R ²³, R ²⁴, R ²⁵and R ²⁶can be hydrogen, and R ²²it can be non-hydrogen substituting group; Or R ²², R ²³, R ²⁵and R ²⁶can be hydrogen, and R ²⁴it can be non-hydrogen substituting group; Alternatively, R ²³, R ²⁵and R ²⁶can be hydrogen, and R ²²and R ²⁴it can be non-hydrogen substituting group; R ²³, R ²⁴and R ²⁵can be hydrogen, and R ²²and R ²⁶it can be non-hydrogen substituting group; Or R ²³and R ²⁵can be hydrogen, and R ²², R ²⁴and R ²⁶it can be non-hydrogen substituting group; Or alternatively, R ²³, R ²⁵and R ²⁶can be hydrogen, and R ²²and R ²⁴it can be non-hydrogen substituting group; Or R ²³, R ²⁴and R ²⁵can be hydrogen, and R ²²and R ²⁶it can be non-hydrogen substituting group.At R, R ²or R ³there is in other embodiment of structure III R ²², R ²³, R ²⁴, R ²⁵and R ²⁶can be hydrogen; Alternatively, R ²³, R ²⁴, R ²⁵and R ²⁶can be hydrogen, and R ²²it can be non-hydrogen substituting group; Alternatively, R ²², R ²⁴, R ²⁵and R ²⁶can be hydrogen, and R ²³it can be non-hydrogen substituting group; Alternatively, R ²², R ²³, R ²⁵and R ²⁶can be hydrogen, and R ²⁴it can be non-hydrogen substituting group; Alternatively, R ²³, R ²⁵and R ²⁶can be hydrogen, and R ²²and R ²⁴it can be non-hydrogen substituting group; Alternatively, R ²³, R ²⁴and R ²⁵can be hydrogen, and R ²²and R ²⁶it can be non-hydrogen substituting group; Alternatively, R ²², R ²⁴and R ²⁶can be hydrogen, and R ²³and R ²⁵it can be non-hydrogen substituting group; Or alternatively, R ²³and R ²⁵can be hydrogen, and R ²², R ²⁴and R ²⁶it can be non-hydrogen substituting group.

In embodiment, can be used as having R, the R of structure III ²or R ³r in group ²², R ²³, R ²⁴, R ²⁵and R ²⁶non-hydrogen substituting group can be halogen, alkyl or-oxyl independently; Alternatively, halogen or alkyl.In some embodiments, can be used as having R, the R of structure III ²or R ³r in group ²², R ²³, R ²⁴, R ²⁵and R ²⁶non-hydrogen substituting group can be halogen, alkyl or alkoxyl group independently.Can be used as substituent halogen, alkyl,-oxyl, alkyl and alkoxyl group in this article by open independently, and can there is ad lib R, the R of structure III for further describing ²and/or R ³group.

On the one hand, R, R ²and R ³can be benzyl, substituted benzyl, 1-phenyl second-1-base independently of one another, replace 1-phenyl second-1-base, 2-phenyl second-1-base or replace 2-phenyl second-1-base.In embodiment, R, R ²and R ³can be benzyl or substituted benzyl independently of one another; Alternatively, 1-phenyl second-1-base or replacement 1-phenyl second-1-base; Alternatively, 2-phenyl second-1-base or replacement 2-phenyl second-1-base; Or alternatively, benzyl, 1-phenyl second-1-base or 2-phenyl second-1-base.In some embodiments, R, R ²and R ³can be benzyl independently of one another; Alternatively, substituted benzyl; Alternatively, 1-phenyl second-1-base; Alternatively, replace 1-phenyl second-1-base; Alternatively, 2-phenyl second-1-base; Or alternatively, replace 2-phenyl second-1-base.

In embodiment, can be used as R, R ²and/or R ³each substituting group of substituted benzyl, 1-phenyl second-1-base or 2-phenyl second-1-base (summarize or concrete) can be halogen, alkyl or-oxyl.In some embodiments, can be used as R, R ²and/or R ³each substituting group of substituted benzyl, 1-phenyl second-1-base or 2-phenyl second-1-base (summarize or concrete) can be halogen, alkyl or alkoxyl group independently.Can be used as substituent halogen, alkyl,-oxyl, alkyl and alkoxyl group in this article by open independently, and can be used as R, R for further describing ad lib ²and/or R ³the substituting group of substituted benzyl, 1-phenyl second-1-base or 2-phenyl second-1-base (summarize or concrete).

On the one hand, R, R ²and R ³can be pyridyl, substituted pyridinyl, furyl, substituted furan base, thienyl or substituted thiophene base independently of one another.

In embodiment, pyridyl (or substituted pyridinyl) R, R ²and/or R ³can be pyridine-2-base, substituted pyridines-2-base, pyridin-3-yl, substituted pyridines-3-base, pyridin-4-yl or substituted pyridines-4-base; Alternatively, pyridine-2-base, pyridin-3-yl or pyridin-4-yl.In some embodiments, pyridyl (or substituted pyridinyl) R, R ²and/or R ³group can be pyridine-2-base or substituted pyridines-2-base; Alternatively, pyridin-3-yl or substituted pyridines-3-base; Alternatively, pyridin-4-yl or substituted pyridines-4-base; Alternatively, pyridine-2-base; Alternatively, substituted pyridines-2-base; Alternatively, pyridin-3-yl; Alternatively, substituted pyridines-3-base; Alternatively, pyridin-4-yl; Or alternatively, substituted pyridines-4-base.In embodiment, substituted pyridinyl R, R ²and/or R ³group can be 2-substituted pyridines-3-base, 4-substituted pyridines-3-base, 5-substituted pyridines-3-base, 6-substituted pyridines-3-base, 2,4-disubstituted pyridines-3-base, 2,6-disubstituted pyridines-3-base or 2,4,6-, tri-substituted pyridines-3-base; Alternatively, 2-substituted pyridines-3-base, 4-substituted pyridines-3-base or 6-substituted pyridines-3-base; Alternatively, 2,4-disubstituted pyridines-3-base or 2,6-disubstituted pyridines-3-base; Alternatively, 2-substituted pyridines-3-base; Alternatively, 4-substituted pyridines-3-base; Alternatively, 5-substituted pyridines-3-base; Alternatively, 6-substituted pyridines-3-base; Alternatively, 2,4-disubstituted pyridines-3-base; Alternatively, 2,6-disubstituted pyridines-3-base; Or alternatively, 2,4,6-, tri-substituted pyridines-3-base.

In embodiment, furyl (or substituted furan base) R, R ²and/or R ³group can be furans-2-base, substituted furan-2-base, furans-3-base or substituted furan-3-base.In embodiment, substituted furan base R, R ²and/or R ³group can be 2-substituted furan-3-base, 4-substituted furan-3-base or 2,4-, bis-substituted furans-3-base.

In embodiment, thienyl (or substituted thiophene base) R, R ²and/or R ³group can be thiophene-2-base, substituted thiophene-2-base, thiene-3-yl-or substituted thiophene-3-base.In some embodiments, thienyl (or substituted thiophene base) R, R ²and/or R ³group can be thiophene-2-base or substituted thiophene-2-base.In embodiment, substituted thiophene base R, R ²and/or R ³group can be 2-substituted thiophene-3-base, 4-substituted thiophene-3-base or 2,4-, bis-substituted thiophenes-3-base.

In embodiment, can be used as R, R ²and/or R ³each substituting group of substituted pyridinyl, furyl or thienyl (summarize or concrete) can be halogen, alkyl or-oxyl independently of one another.In some embodiments, can be used as R, R ²and R ³substituted pyridinyl, furyl and/or or each substituting group of thienyl (summarize or concrete) can be halogen, alkyl or alkoxyl group independently of one another; Alternatively, halogen or alkyl; Alternatively, halogen or alkoxyl group; Alternatively, alkyl or alkoxyl group; Alternatively, halogen; Alternatively, alkyl; Or alternatively, alkoxyl group.Can be used as substituent halogen, alkyl,-oxyl, alkyl and alkoxyl group in this article by open independently, and can be used as R, R for further describing ad lib ²and/or R ³the substituting group of substituted pyridinyl, furyl and/or thienyl (summarize or concrete).

In non-limiting embodiment, R, R ²and/or R ³can be phenyl, 2-alkyl phenyl, 3-alkyl phenyl, 4-alkyl phenyl, 2 independently of one another, 4-dialkyl phenyl organic, 2,6-dialkyl phenyl organic, 3,5-dialkyl phenyl organic or 2,4,6-trialkyl phenyl; Alternatively, 2-alkyl phenyl, 4-alkyl phenyl, 2,4-dialkyl phenyl organic, 2,6-dialkyl phenyl organic or 2,4,6-trialkyl phenyl.In another non-limiting embodiment, R, R ²and R ³can be phenyl, 2-alkoxyl phenyl, 3-alkoxyl phenyl, 4-alkoxyl phenyl or 3,5-dialkoxy phenyl independently of one another.In other non-limiting embodiment, R, R ²and R ³can be phenyl, 2-halobenzene base, 3-halobenzene base, 4-halobenzene base, 2 independently of one another, 6-dihalo-phenyl or 3,5-dialkyl phenyl organic; Alternatively, 2-halobenzene base, 4-halobenzene base or 2,6-dihalo-phenyl; Alternatively, 2-halobenzene base or 4-halobenzene base; Alternatively, 3-halobenzene base or 3,5-dihalo-phenyl; Alternatively, 2-halobenzene base; Alternatively, 3-halobenzene base; Alternatively, 4-halobenzene base; Alternatively, 2,6-dihalo-phenyl; Or alternatively, 3,5-dihalo-phenyl.Halogen root, alkyl substituent and alkoxy substituent are described in this article independently, and can be used for R, R for further describing ad lib ²and/or R ³alkyl phenyl, dialkyl phenyl organic, trialkyl phenyl, alkoxyl phenyl, dialkoxy phenyl, halobenzene base or dihalo-phenyl.Generally, halogen root, alkyl substituent or the alkoxy substituent of dialkyl group, trialkyl phenyl, dialkoxy phenyl or dihalo-phenyl can be identical; Or alternatively, halogen, alkyl substituent or the alkoxy substituent of alkyl phenyl, dialkyl phenyl organic, trialkyl phenyl, dialkoxy phenyl or dihalo-phenyl can be different.

In non-limiting embodiment, R, R ²and R ³can be 2-aminomethyl phenyl, 2-ethylphenyl, 2-isopropyl phenyl, 2-tert-butyl-phenyl, 4-aminomethyl phenyl, 4-ethylphenyl, 4-isopropyl phenyl or 4-tert-butyl-phenyl independently of one another; Alternatively, 2-aminomethyl phenyl, 2-ethylphenyl, 2-isopropyl phenyl or 2-tert-butyl-phenyl; Alternatively, 4-aminomethyl phenyl, 4-ethylphenyl, 4-isopropyl phenyl or 4-tert-butyl-phenyl; Alternatively, 2-aminomethyl phenyl; Alternatively, 2-ethylphenyl; Alternatively, 2-isopropyl phenyl; Alternatively, 2-tert-butyl-phenyl; Alternatively, 4-aminomethyl phenyl; Alternatively, 4-ethylphenyl; Alternatively, 4-isopropyl phenyl; Or alternatively, 4-tert-butyl-phenyl.In another non-limiting embodiment, R, R ²and R ³can be 2-p-methoxy-phenyl, 2-ethoxyl phenenyl, 2-isopropyl phenyl, 2-tert.-butoxy phenyl, 4-p-methoxy-phenyl, 4-ethoxyl phenenyl, 4-isopropyl phenyl or 4-tert.-butoxy phenyl independently of one another; Alternatively, 2-p-methoxy-phenyl, 2-ethoxyl phenenyl, 2-isopropyl phenyl or 2-tert.-butoxy phenyl; Alternatively, 4-p-methoxy-phenyl, 4-ethoxyl phenenyl, 4-isopropyl phenyl or 4-tert.-butoxy phenyl; Alternatively, 2-p-methoxy-phenyl; Alternatively, 2-ethoxyl phenenyl; Alternatively, 2-isopropyl phenyl; Alternatively, 2-tert.-butoxy phenyl; Alternatively, 4-p-methoxy-phenyl; Alternatively, 4-ethoxyl phenenyl; Alternatively, 4-isopropyl phenyl; Or alternatively, 4-tert.-butoxy phenyl.In other non-limiting embodiment, R, R ²and R ³can be 2-fluorophenyl, 2-chloro-phenyl-, 3-fluorophenyl, 3-chloro-phenyl-, 4-fluorophenyl, 4-chloro-phenyl-, 3 independently of one another, 5-difluorophenyl or 3,5-dichlorophenyl; Alternatively, 2-fluorophenyl or 2-chloro-phenyl-; Alternatively, 3-fluorophenyl or 3-chloro-phenyl-; Alternatively, 4-fluorophenyl or 4-chloro-phenyl-; Alternatively, 3,5-difluorophenyl or 3,5-dichlorophenyl; Alternatively, 3-fluorophenyl, 3-chloro-phenyl-, 3,5-difluorophenyl or 3,5-dichlorophenyl; Alternatively, 3-fluorophenyl or 3,5-difluorophenyl; Alternatively, 2-fluorophenyl; Alternatively, 2-chloro-phenyl-; Alternatively, 3-fluorophenyl; Alternatively, 3-chloro-phenyl-; Alternatively, 4-fluorophenyl; Alternatively, 4-chloro-phenyl-; Alternatively, 3,5-difluorophenyl; Or alternatively, 3,5-dichlorophenyl.

In embodiment, Q is donor groups, and it can have structure (II), (III) or (IV):

Wherein N represents nitrogen, and Z can be oxygen or sulphur, and R ⁴can be hydrogen, halogen, alkyl or substituted hydrocarbon radical.Generally, R ⁴can be herein (for example,, at the applicable R that does ²and/or R ³group describe in) describe halogen, alkyl or substituted hydrocarbon radical in any.

In embodiment, CATCOMP comprises metal salt complex, alternatively, and the metal salt complex of two (phenol) compounds of imines; Alternatively, can there is the metal salt complex of two (phenol) compounds of imines of structure V.

In structure V, O and N represent respectively oxygen and nitrogen, and Q represents donor groups, and it can have structure (VI), (VII) or (VIII).

And M is the 3rd family's to the 12 group 4 transition metals or lanthanon.About structure V, X ⁰can be neutral ligand, and a have 0,1 or 2 value; X ¹can be single anion ligand, and b have 0,1,2,3 or 4 value; And X ²can be two anion ligands, and c have 0 or 1 value.

In embodiment, the R of structure V, R ², R ³, R ⁴correspond respectively to R, the R of structure I with Q ², R ³, R ⁴, and Q, makes the R of description scheme I ², R ³, R ⁴, and Q group, feature and aspect used can be used for corresponding R, the R of description scheme V ², R ³, R ⁴and Q.R, R ², R ³and R ⁴in one or more can be identical or different separately.

Generally, the atoms metal (for example, the M in structure V) of the metal salt complex of two (phenol) compounds of imines can be any atoms metal.On the one hand, the atoms metal of metal-salt can be transition metal or lanthanon.In embodiment, it is following or mainly by forming below that suitable metal-salt can comprise: 3-12 group 4 transition metal; Alternatively, 4-10 group 4 transition metal; Alternatively, 6-9 group 4 transition metal; Alternatively, 7-8 group 4 transition metal; Alternatively, the 4th group 4 transition metal; Alternatively, the 5th group 4 transition metal alternatively, the 6th group 4 transition metal; Alternatively, the 7th group 4 transition metal; Alternatively, the 8th group 4 transition metal; Alternatively, the 9th group 4 transition metal; Or alternatively, the 10th group 4 transition metal.In some embodiments, metal-salt can comprise titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium, platinum, copper or zinc.Alternatively, M is the 4th group 4 transition metal.Alternatively, M is titanium.Alternatively, M is zirconium.Alternatively, M is hafnium.

Generally, the atoms metal of metal can have the arbitrarily positive oxidation state that can be used for atoms metal.In embodiment, the oxidation state of M equals (b+2c+2).In embodiment, the oxidation state of transition metal can be+2 to+6; Alternatively ,+2 to+4; Or alternatively ,+2 to+3.In some embodiments, transition metal salt ML _nthe oxidation state of atoms metal can be+1; Alternatively ,+2; Alternatively ,+3; Or alternatively ,+4.For example, the most common oxidation state of Ti, Zr and Hf can be+4; Therefore, c can equal zero and b can equal 2 (two single anion ligands), or b can equal zero and c can equal 1 (two anion ligands).The most common oxidation state of V and Ta can be+5; Therefore, for example, b can equal 1 (single anion ligand) and c can equal 1 (two anion ligands).

About structure V, X ⁰can be neutral ligand, and integer a in structure V can be 0,1 or 2.On the one hand, suitable neutral ligand can comprise σ-donor solvent, this σ-donor solvent comprise can with structure V in the atom (one or more) of atoms metal coordination.The example of suitable ligating atom includes but not limited to the combination of O, N, S and P or these atoms.Neutral ligand can not be substituted maybe and can be substituted.Substituting group is described in this article independently, and can be ad lib for further describing the X that can be used as structure V ⁰neutral ligand.In certain aspects, neutral ligand can be Lewis alkali.In the time that integer a equals 2, consider that two neutral ligands can be identical or different, and the description of carrying out is applicable to each part independently herein.

On the one hand, X ⁰can be ether, thioether, amine, nitrile or phosphine.On the other hand, X ⁰can be acyclic ethers, have cyclic ethers, acyclic thioether, have epithio ether, nitrile, without cyclammonium, have cyclammonium, acyclic phosphine, have ring phosphine or its combination.In other side, X ⁰can be acyclic ethers or have cyclic ethers; Alternatively, acyclic thioether or have epithio ether; Alternatively, without cyclammonium or there is cyclammonium; Alternatively, acyclic phosphine or have ring phosphine; Alternatively, acyclic ethers; Alternatively, there is cyclic ethers; Alternatively, acyclic thioether; Alternatively, there is epithio ether; Alternatively, nitrile; Alternatively, without cyclammonium; Alternatively, there is cyclammonium; Alternatively, acyclic phosphine; Or alternatively, there is ring phosphine.Further, X ⁰can comprise any acyclic ethers, have cyclic ethers, acyclic thioether, have epithio ether, nitrile, without cyclammonium, have cyclammonium, acyclic phosphine or have any replacement analogue of ring phosphine, as open herein.

On the one hand, X ⁰can be to there is formula R ^1qthe nitrile of C=N, there is formula R ^2q-O-R ^3qether, there is formula R ^4q-S-R ^5qthioether, there is formula NR ^6qr ^7qr ^8q, NHR ^6qr ^7qor NH ₂r ^6qamine or there is formula PR ^9qr ^10qr ^11q, pHR ^9qr ^10qor PH ₂r ^9qphosphine; Alternatively, there is formula R ^1qthe nitrile of C ≡ N, there is formula R ^2q-O-R ^3qether, there is formula R ^4q-S-R ^5qthioether, there is formula NR ^6qr ^7qr ^8qamine or there is formula pR ^9qr ^10qr ^11qphosphine; Or alternatively, there is formula R ^1qthe nitrile of C ≡ N, there is formula R ^2q-O-R ^3qether, there is formula R ^4q-S-R ^5qthioether, there is formula NR ^6qr ^7qr ^8qamine or there is formula PR ^9qr ^10qr ^11qphosphine.On the one hand, X ⁰can be to there is formula R ^1qthe nitrile of C=N; Alternatively, there is formula R ^2q-O-R ^3qether; Alternatively, there is formula R ^4a-S-R ^5athioether; Alternatively, there is formula NR ^6qr ^7qr ^8q, NHR ^6qr ^7qor NH ₂r ^6qamine; Alternatively, there is formula PR ^9qr ^10qr ^11q, PHR ^9qr ^10qor PH ₂r ^9qphosphine; Or alternatively, there is formula PR ^9qr ^10qr ^11qphosphine.

On the one hand, there is formula R ^1qthe R of the nitrile of C=N ^1q, there is formula R ^2q-O-R ^3qthe R of ether ^2qand R ^3q, there is formula R ^4q-S-R ^5qthe R of thioether ^4qand R ^5q, there is formula NR ^6qr ^7qr ^8q, NHR ^6qr ^7qor NH ₂r ^6qthe R of amine ^6q, R ^7qand R ^8qand there is formula PR ^9qr ^10qr ^11q, PHR ^9qr ^10qor PH ₂r ^9qthe R of phosphine ^9q, R ^10qand R ^11qcan be C independently ₁to C ₁₈alkyl; Alternatively, C ₁to C ₁₅alkyl; Alternatively, C ₁to C ₁₂alkyl; Alternatively, C ₁to C ₈alkyl; Or alternatively, C ₁to C ₆alkyl.It shall yet further be noted that and there is formula R ^2q-O-R ^3qthe R of ether ^2qand R ^3q, there is formula R ^4q-S-R ^5qthe R of thioether ^4qand R ^5q, there is formula NR ^6qr ^7qr ^8qor NHR ^6qr ^7qthe R of amine ^6q, R ^7qand R ^8qin any two and/or there is formula pR ^9qr ^10qr ^11qor PHR ^9qr ^10qthe R of phosphine ^9q, R ^10qand R ^11qin any two can be in conjunction with, form respectively the ring that comprises ether oxygen atom, thioether sulphur atom, amine nitrogen atom or phosphine phosphorus atom, thereby be formed with cyclic ethers, thioether, amine or phosphine, as herein about having as described in cyclic ethers, thioether, amine and phosphine.

On the one hand, there is formula R ^1qthe R of the nitrile of C=N ^1q, there is formula R ^2q-O-R ^3qthe R of ether ^2qand R ^3q, there is formula R ^4q-S-R ^5qthe R of thioether ^4qand R ^5q, there is formula NR ^6qr ^7qr ^8q, NHR ^6qr ^7qor NH ₂r ^6qthe R of amine ^6q, R ^7qand R ^8qand there is formula PR ^9qr ^10qr ^11q, PHR ^9qr ^10qor PH ₂r ^9qthe R of phosphine ^9q, R ^10qand R ^11qany alkyl disclosed herein independently.Alkyl can be for example any alkyl disclosed herein, cycloalkyl, aryl or aralkyl.

On the other hand, the X in structure V ⁰can be C independently ₂-C ₃₀ether, C ₂-C ₃₀thioether, C ₂-C ₂₀nitrile, C ₁-C ₃₀amine or C ₁-C ₃₀phosphine; Alternatively, C ₂-C ₁₈ether; Alternatively, C ₂-C ₁₈thioether; Alternatively, C ₂-C ₁₂nitrile; Alternatively, C ₁-C ₁₈amine; Or alternatively, C ₁-C ₁₈phosphine.In certain aspects, each neutral ligand can be C independently ₂-C ₁₂ether, C ₂-C ₁₂thioether, C ₂-C ₈nitrile, C ₁-C ₁₂amine or C ₁-C ₁₂phosphine; Alternatively, C ₂-C ₁₀ether; Alternatively, C ₂-C ₁₀thioether; Alternatively, C ₂-C ₆nitrile; Alternatively, C ₁-C ₈amine; Or alternatively, C ₁-C ₈phosphine.

Can be used as alone or in combination X ⁰suitable ether can include but not limited to dimethyl ether, Anaesthetie Ether, dipropyl ether, dibutyl ether, methyl ethyl ether, methyl-propyl ether, methyl butyl ether, diphenyl ether, xylyl ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, 2,3-dihydrofuran, 2,5-dihydrofuran, furans, cumarone, isobenzofuran, diphenylene-oxide, tetrahydropyrans, 3,4-dihydro-2H-pyrans, 3,6-dihydro-2H-pyrans, 2H-pyrans, 4H-pyrans, 1,3-bis- alkane, 1,4-bis- alkane, morpholine etc., comprise its substitutive derivative.

Can be used as alone or in combination X ⁰suitable thioether can comprise but not limit, dimethyl thioether, diethyl thioether, dipropyl thioether, butyl sulfide, methylethyl thioether, methyl-propyl thioether, methyl butyl sulfide, diphenylsulfide, xylyl thioether, thiophene, thionaphthene, tetramethylene sulfide, tetrahydric thiapyran (thiane) etc., comprise its substitutive derivative.

Can be used as alone or in combination X ⁰suitable nitrile can include but not limited to acetonitrile, propionitrile, butyronitrile, benzonitrile, 4-methyl benzonitrile etc., comprise its substitutive derivative.

Can be used as alone or in combination X ⁰suitable amine can include but not limited to methylamine, ethylamine, propyl group amine, butylamine, dimethyl amine, diethylamide, dipropylamine, dibutylamine, Trimethylamine, triethylamine, tripropylamine, tributylamine, aniline, diphenylamine, triphenylamine, tolyl amine, xylyl amine, xylyl amine, pyridine, quinoline, pyrroles, indoles, 2-picoline, 3-picoline, 4-picoline, 2,5-dimethyl pyrrole, 2,5-diethyl pyrroles, 2,5-dipropyl pyrroles, 2,5-dibutyl pyrroles, 2,4-dimethyl pyrrole, 2,4-diethyl pyrroles, 2,4-dipropyl pyrroles, 2,4-dibutyl pyrroles, 3,4-dimethyl pyrrole, 3,4-diethyl pyrroles, 3,4-dipropyl pyrroles, 3,4-dibutyl pyrroles, 2-methylpyrrole, 2-N-ethyl pyrrole N-, 2-propyl pyrrole, 2-butyl pyrroles, 3-methylpyrrole, 3-N-ethyl pyrrole N-, 3-propyl pyrrole, 3-butyl pyrroles, 3-ethyl-2,4-dimethyl pyrrole, 2,3,4,5-tetramethyl-pyrroles, 2,3,4,5-tetraethyl-pyrroles etc., comprise its substitutive derivative.Suitable amine can be primary amine, secondary amine or tertiary amine.

Can be used as alone or in combination X ⁰suitable phosphine can include but not limited to trimethyl-phosphine, triethyl phosphine, tripropyl phosphine, tributylphosphine, Phenylphosphine, tolylphosphine, diphenylphosphine, xylyl phosphine, triphenylphosphine, trimethylphenyl phosphine, methyldiphenyl base phosphine, dimethylphenylphosphine, ethyl diphenylphosphine, diethyl phenyl phosphine etc., comprise its substitutive derivative.

On the one hand, X ⁰can be azetidine, trimethylene oxide, Thietane (thietane), dioxetane, dithietane, Pyrrolidine, pyrrolin, pyrroles, indoles, isoindole, tetrahydrofuran (THF), 2-methyltetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, dihydrofuran, furans, cumarone, isobenzofuran, tetramethylene sulfide, dihydro-thiophene, thiophene, thionaphthene, different thionaphthene, imidazolidine, pyrazoles, imidazoles, azoles alkane, azoles, different azoles, thiazolidine, thiazole, isothiazole, benzothiazole, dioxolane, dithiolane, triazole, dithiazole, piperidines, pyridine, dimethyl amine, diethylamide, tetrahydropyrans, dihydropyrane, pyrans, thiophene alkane, piperazine, diazine, piperazine, thiazine, dithiane, two alkane, two english, triazine, triazine alkane (triazinane), three alkane, heptan is because, azepines, thiophene heptan is because of, two azepines, morpholine, quinoline, tetrahydrochysene quinone, two ring [3.3.1] tetrasiloxane or acetonitriles; Alternatively, azetidine, trimethylene oxide, Thietane, dioxetane, dithietane, Pyrrolidine, tetrahydrofuran (THF), 2-methyltetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, tetramethylene sulfide, imidazolidine, azoles alkane, azoles, thiazolidine, thiazole, dioxolane, dithiolane, piperidines, tetrahydropyrans, pyrans, thiophene alkane, piperazine, piperazine, thiazine, dithiane, two alkane, two english, triazine alkane, three alkane, azepines, thiophene heptan is because of, two azepines, morpholine, 1,2-thiazole or two ring [3.3.1] tetrasiloxanes; Alternatively, Pyrrolidine, tetrahydrofuran (THF), 2-methyltetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, tetramethylene sulfide, azoles alkane, thiazolidine, dioxolane, dithiolane, dithiazole, piperidines, tetrahydropyrans, pyrans, thiophene alkane, piperazine, dithiane, two alkane, two english, three alkane or morpholine; Alternatively, tetrahydrofuran (THF), 2-methyltetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, tetramethylene sulfide, dioxolane, dithiolane, tetrahydropyrans, pyrans, thiophene alkane, dithiane, two alkane, two english or three alkane; Alternatively, tetrahydrofuran (THF), dioxolane, tetrahydropyrans, two alkane or three alkane; Alternatively, pyrroles, furans, pyrazoles, imidazoles, azoles, different azoles, thiazole, isothiazole, triazole, pyridine, dimethyl amine, diethylamide, diazine, triazine or quinoline; Alternatively, pyrroles, furans, imidazoles, azoles, thiazole, triazole, pyridine, dimethyl amine, diethylamide, diazine or triazine; Or alternatively, furans, azoles, thiazole, triazole, pyridine, diazine or triazine.In certain aspects, X ⁰it can be azetidine; Alternatively, trimethylene oxide; Alternatively, Thietane; Alternatively, dioxetane; Alternatively, dithietane; Alternatively, Pyrrolidine; Alternatively, pyrrolin, alternatively, pyrroles; Alternatively, indoles; Alternatively, isoindole; Alternatively, tetrahydrofuran (THF); Alternatively, 2-methyltetrahydrofuran; Alternatively, 2,5-dimethyl-tetrahydrofuran; Alternatively, pyrrolin; Alternatively, furans; Alternatively, cumarone; Alternatively, isobenzofuran; Alternatively, tetramethylene sulfide; Alternatively, dihydro-thiophene; Alternatively, thiophene; Alternatively, thionaphthene; Alternatively, different thionaphthene; Alternatively, imidazolidine; Alternatively, pyrazoles; Alternatively, imidazoles; Alternatively, azoles alkane; Alternatively, azoles; Alternatively, different azoles; Alternatively, thiazolidine; Alternatively, thiazole; Alternatively, benzothiazole; Alternatively, isothiazole; Alternatively, dioxolane; Alternatively, dithiolane; Alternatively, triazole; Alternatively, dithiazole; Alternatively, piperidines; Alternatively, pyridine; Alternatively, dimethyl amine; Alternatively, diethylamide; Alternatively, tetrahydropyrans; Alternatively, dihydropyrane; Alternatively, pyrans; Alternatively, thiophene alkane; Alternatively, piperazine; Alternatively, diazine; Alternatively, piperazine; Alternatively, thiazine; Alternatively, dithiane; Alternatively, two alkane; Alternatively, two english; Alternatively, triazine; Alternatively, triazinane; Alternatively, three alkane; Alternatively, heptan because of; Alternatively, azepines; Alternatively, thiophene heptan because of; Alternatively, two azepines; Alternatively, morpholine; Alternatively, quinoline; Alternatively, tetrahydrochysene quinone; Alternatively, two ring [3.3.1] tetrasiloxanes; Or alternatively, acetonitrile.

On the other hand, X ⁰can be azetidine, Pyrrolidine, pyrrolin, pyrroles, indoles, isoindole, imidazolidine, pyrazoles, imidazoles, azoles alkane, azoles, different azoles, thiazolidine, thiazole, isothiazole, three , benzotriazole, dithiazole, piperidines, pyridine, dimethyl amine, diethylamide, piperazine, diazine, piperazine, thiazine, triazine, azepines, two azepines, morpholine, quinoline or tetrahydroisoquinoline.X on the other hand, ⁰can be Thietane, dithietane, tetramethylene sulfide, dihydro-thiophene, thiophene, thionaphthene, different thionaphthene, thiazolidine, thiazole, isothiazole, dithiolane, dithiazole, thiophene alkane, thiazine, dithiane or thiophene heptan because of.On the other hand, X ⁰can be tetrahydrofuran (THF), furans, methyltetrahydrofuran, dihydrofuran, tetrahydropyrans, 2,3-dihydropyrane, 1,3-bis- alkane, Isosorbide-5-Nitrae-bis- alkane, morpholine, N-methylmorpholine, acetonitrile, propionitrile, butyronitrile, benzonitrile, pyridine, ammonia, methylamine, ethylamine, dimethyl amine, diethylamide, Trimethylamine, triethylamine, trimethyl-phosphine, triethyl phosphine, triphenylphosphine, tri-n-butyl phosphine, methyl isonitrile, normal-butyl isonitrile, phenyl isonitrile, SMe2, thiophene or tetramethylene sulfide.On the other hand, X ⁰can be tetrahydrofuran (THF), methyltetrahydrofuran, tetrahydropyrans, Isosorbide-5-Nitrae-bis- alkane, acetonitrile, pyridine, dimethyl amine, diethylamide, ammonia, Trimethylamine, triethylamine, trimethyl-phosphine, triethyl phosphine, triphenylphosphine, SMe ₂or tetramethylene sulfide; Alternatively, tetrahydrofuran (THF), methyltetrahydrofuran, tetrahydropyrans or Isosorbide-5-Nitrae-bis- alkane; Alternatively, ammonia, Trimethylamine or triethylamine; Or alternatively, trimethyl-phosphine, triethyl phosphine or triphenylphosphine.Also on the other hand, X ⁰can be tetrahydrofuran (THF), acetonitrile, pyridine, ammonia, dimethyl amine, diethylamide, Trimethylamine, trimethyl-phosphine or triphenylphosphine; Alternatively, tetrahydrofuran (THF), acetonitrile, pyridine, dimethyl amine, diethylamide, Trimethylamine, trimethyl-phosphine or triphenylphosphine; Alternatively, tetrahydrofuran (THF), acetonitrile, dimethyl amine, diethylamide or pyridine; Alternatively, tetrahydrofuran (THF); Alternatively, acetonitrile; Alternatively, dimethyl amine; Alternatively, diethylamide; Or alternatively, pyridine.

X in structure V ¹can be single anion ligand, and integer b in structure V can be 0,1,2,3 or 4.X ¹can be hydrogen (hydrogen root), halogen root, C ₁to C ₁₈the amino silyl of alkyl,-oxyl, alkyl amino, alkyl silyl or alkyl.If b is greater than 1, each X of structure V ¹group can be identical or different.In embodiment, b is greater than 1 and each X ¹can be hydrogen (hydrogen root), halogen root, C independently ₁to C ₁₈the amino silyl of alkyl,-oxyl, alkyl amino, alkyl silyl or alkyl.

On the one hand, X ¹can be hydrogen, halogen root (for example, F, Cl, Br or I), C ₁to C ₁₈the amino silyl of alkyl,-oxyl, alkyl amino, alkyl silyl or alkyl.On the other hand, X ¹can be hydrogen, halogen root, C ₁to C ₁₂the amino silyl of alkyl,-oxyl, alkyl amino, alkyl silyl or alkyl.Also on the other hand, X ¹can be hydrogen, halogen root, C ₁to C ₁₀the amino silyl of alkyl,-oxyl, alkyl amino, alkyl silyl or alkyl.Again on the other hand, X ¹can be hydrogen, halogen root, C ₁to C ₈the amino silyl of alkyl,-oxyl, alkyl amino, alkyl silyl or alkyl.

Can be the X in structure V ¹alkyl can be any C disclosed herein ₁to C ₁₈alkyl, any C ₁to C ₁₂alkyl, any C ₁to C ₁₀alkyl or arbitrarily C ₁to C ₈alkyl.-oxyl is used by generality in this article, for example comprise alkoxyl group, aryloxy and-(alkyl or aryl)-O-(alkyl or aryl group), and these groups for example can comprise, up to about 18 carbon atom (, C ₁to C ₁₈, C ₁to C ₁2, C ₁to C ₁₀or C ₁to C ₈-oxyl).Exemplary and the limiting examples of-oxyl can comprise methoxyl group, oxyethyl group, propoxy-, butoxy, phenoxy group, substituent phenoxy, methyl ethyl diketone acid group (acac) etc.Term alkyl amino is used by generality in this article, system such as refer to alkylamino, arylamino, dialkyl amido, ammonia diaryl base and-(alkyl or aryl)-N-(alkyl or aryl) group etc.Unless illustrated in addition, can be the X in structure V ¹alkyl amino for example can comprise, up to about 18 carbon atom (, C ₁to C ₁₈, C ₁to C ₁₂, C ₁to C ₁₀or C ₁to C ₈alkyl amino).Can be the X in structure V ¹alkyl silyl can be any C disclosed herein ₁to C ₁₈alkyl silyl, any C ₁to C ₁₂alkyl silyl, any C ₁to C ₁₀alkyl silyl or arbitrarily C ₁to C ₈alkyl silyl.The amino silyl of alkyl is used in this article, means the group that comprises at least one hydrocarbon part, at least one nitrogen-atoms and at least one Siliciumatom.Can be X ¹can include but not limited to-N of the exemplary and limiting examples (SiMe of the amino silyl of alkyl ₃) ₂,-N (SiEt ₃) ₂deng.Unless illustrated in addition, can be X ¹the amino silyl of alkyl for example can comprise, up to about 18 carbon atom (, C ₁to C ₁₈, C ₁to C ₁₂, C ₁to C ₁₀or C ₁to C ₈the amino silyl of alkyl).

According to an aspect of the present invention, the X in structure V ¹it can be halogen root; Alternatively, C ₁to C ₁₈alkyl; Alternatively, C ₁to C ₁₈-oxyl; Alternatively, C ₁to C ₁₈alkyl amino; Alternatively, C ₁to C ₁₈alkyl silyl; Or alternatively, C ₁to C ₁₈the amino silyl of alkyl.According on the other hand, X ¹can be hydrogen; Alternatively, F; Alternatively, Cl; Alternatively, Br; Alternatively, I; Alternatively, C ₁to C ₁₈alkyl; Alternatively, C ₁to C ₁₈-oxyl; Alternatively, C ₁to C ₁₈alkyl amino; Alternatively, C ₁to C ₁₈alkyl silyl; Or alternatively, C ₁to C ₁₈the amino silyl of alkyl.According to more on the one hand, at least one X ¹it can be the amino silyl of hydrogen, halogen root, methyl, phenyl, benzyl, alkoxyl group, aryloxy, methyl ethyl diketone acid group, alkylamino, dialkyl amido, trialkyl silyl or alkyl; Alternatively, hydrogen, halogen root, methyl, phenyl or benzyl; Alternatively, alkoxyl group, aryloxy or methyl ethyl diketone acid group; Alternatively, alkylamino or dialkyl amido; Alternatively, the amino silyl of trialkyl silyl or alkyl; Alternatively, hydrogen or halogen root; Alternatively, methyl, phenyl, benzyl, alkoxyl group, aryloxy, methyl ethyl diketone acid group, alkylamino or dialkyl amido; Alternatively, hydrogen; Alternatively, halogen root; Alternatively, methyl; Alternatively, phenyl; Alternatively, benzyl; Alternatively, alkoxyl group; Alternatively, aryloxy; Alternatively, methyl ethyl diketone acid group; Alternatively, alkylamino; Alternatively, dialkyl amido; Alternatively, trialkyl silyl; Or alternatively, the amino silyl of alkyl.In aspect these and other, the amino silyl of alkoxyl group, aryloxy, alkylamino, dialkyl amido, trialkyl silyl and alkyl can be C ₁to C ₁₈, C ₁to C ₁₂, C ₁to C ₁₀or C ₁to C ₈the amino silyl of alkoxyl group, aryloxy, alkylamino, dialkyl amido, trialkyl silyl or alkyl.

X in structure V ²can be two anion ligands, and integer c in structure V can be 0 or 1.On the one hand, X ²can be=O ,=NR ^2Aor=CR ^2Br ^2C.On the other hand, X ²can be=O; Alternatively, X ²can be=NR ^2A; Or alternatively, X ²can be=CR ^2Br ^2C.Independently, R ^2A, R ^2Band R ^2Ccan be hydrogen or any C disclosed herein ₁to C ₁₈alkyl; Alternatively, hydrogen or any C disclosed herein ₁to C ₁₂alkyl; Alternatively, hydrogen or any C disclosed herein ₁to C ₁₀alkyl; Or alternatively, hydrogen or any C disclosed herein ₁to C ₈alkyl.As an example, R ^2A, R ^2Band R ^2Ccan be hydrogen or any C disclosed herein independently of one another ₁to C ₁₂, C ₁to C ₈or any C ₁to C ₆alkyl.

In embodiment, imines (two) phenolic compound that is applicable to CATCOMP of the present disclosure comprises the compound with structure I X:

The wherein R of description scheme I, R ²and R ³group used can be respectively used to R, the R of description scheme IX ²and R ³.

In embodiment, two (phenol) compounds of imines that are applicable to CATCOMP of the present disclosure comprise the compound with structure X:

The wherein R of description scheme I and R ²group used can be respectively used to R and the R of description scheme X ².In the embodiment of structure X, R is the tertiary butyl, R ²hydrogen.Alternatively, R and R ²it is the tertiary butyl; Alternatively, R is methyl, R ²hydrogen; Alternatively, R and R ²it is chlorine root; Alternatively, R is adamantyl and R ²it is methyl; Alternatively, R is methoxyl group, R ²hydrogen; Or alternatively, R and R ²hydrogen.

In embodiment, the imines phenolic compound that is applicable to CATCOMP of the present disclosure comprises the compound with structure XI:

The wherein R of description scheme I, R ²and R ³group used can be respectively used to R, the R of description scheme XI ²and R ³.

In embodiment, the imines phenolic compound that is applicable to CATCOMP of the present disclosure comprises the compound with structure XII:

The wherein R of description scheme I and R ²group used can be respectively used to R and the R of description scheme XII ².In the embodiment of structure XII, R and R ²it is methyl; Or alternatively, R is methoxyl group, R ²hydrogen.

In embodiment, the metal salt complex that is applicable to imines (two) phenolic compound of CATCOMP of the present disclosure comprises the compound with structure XIII:

Wherein M is titanium, zirconium or hafnium, R, R ², R ³, X ⁰and X ¹there is type described herein, and X ⁰optional.In the embodiment of structure XIII, M is zirconium, and R is the tertiary butyl.Alternatively, M is hafnium, and R is the tertiary butyl; Alternatively, M is zirconium, R and R ²it is the tertiary butyl; Alternatively, M is zirconium, and R is methyl; Alternatively, M is zirconium, R and R ²it is chloro; Or alternatively, M is zirconium, R is adamantyl, R ²it is methyl.

In embodiment, the metal salt complex that is applicable to two (phenol) compounds of imines of CATCOMP of the present disclosure comprises the compound with structure XIV:

The wherein R of description scheme I and R ²group used can be respectively used to R and the R of description scheme XIV ², and Et ₂o is optional.

In embodiment, the metal salt complex that is applicable to two (phenol) compounds of imines of CATCOMP of the present disclosure comprises the compound with structure XV, wherein Et ₂o is optional:

In embodiment, the metal salt complex that is applicable to two (phenol) compounds of imines of CATCOMP of the present disclosure comprises the compound in structure XVI, XVII, XVIII, XIX, XX or XXI with any::

In embodiment, the containing metal cyclopentadinyl compound in CATCOMP is when the ethylene rolymerization catalyst being bridged metallocene not, called after MTE-A.At this, term " metallocenes " is described and is comprised at least one η ³to η ⁵the compound of-cycloalkadienyl type part, wherein η ³to η ⁵-cycloalkadienyl part comprises cyclopentadienyl ligands, indenyl ligands, fluorenyl ligand etc., comprises in these fractional saturation or substitutive derivative or analogue of any.Substituting group possible on these parts comprises hydrogen, and therefore in the disclosure, the statement of " its substitutive derivative " comprises fractional saturation part, as tetrahydro indenyl, tetrahydrofluorenyl, octahydrofluorenyl; Fractional saturation indenyl; Fractional saturation fluorenyl; Replace fractional saturation indenyl; Replace fractional saturation fluorenyl etc.

In embodiment, MTE-A is can be by wherein a kind of compound of sign of general formula 1 or 2:

Wherein each X is F, C1, Br, I, methyl, benzyl, phenyl, H, BH independently ₄, have 20 carbon atoms nearly-oxyl, have 20 carbon atoms nearly alkyl amino, there is nearly trialkyl silyl, the OBR' of 20 carbon atoms ₂---wherein R ' has to reach the alkyl of 12 carbon atoms or have the nearly aryl of 12 carbon atoms, and SO ₃r "---wherein R " can be to have to reach the alkyl of 12 carbon atoms or there is the nearly aryl of 12 carbon atoms; Y is CR ₂or SiR ₂group, wherein R is hydrogen or alkyl; Cp ^a, Cp ^b, Cp ^cand Cp ^dto replace or unsubstituted ring pentadienyl, indenyl or fluorenyl independently of one another, and Cp wherein ^a, Cp ^b, Cp ^cand Cp ^don any substituting group can be H, there is the alkyl of 18 carbon atoms nearly or there is the nearly alkyl silyl of 18 carbon atoms.

In embodiment, MTE-A is binuclear compound, the identical constitutional features that wherein each metal part is explained before having herein.In embodiment, MTE-A is non-bridged metallocene.Be applicable in the disclosure to be represented by structure (1)-(13) as the limiting examples of the compound of MTE-A:

Other limiting examples that can suitably be used as the Metallocenic compound of the MTE-A in the CATCOMP that discloses type herein comprises molybdenyl dichloride (cyclopentadienyl) hafnium; Two (n-butyl cyclopentadienyl) two (di-t-butyl amido) hafnium; Molybdenyl dichloride (n-propyl cyclopentadienyl) zirconium; Molybdenyl dichloride (pentamethyl-cyclopentadienyl) zirconium; Molybdenyl dichloride (1-propyl group indenyl) zirconium; Or its arbitrary combination.

In optional embodiment, CATCOMP comprises bridged metallocene compounds, and it is named as MTE-B hereinafter.In embodiment, MTE-B can be by general formula 3 or 4 one of them sign:

Wherein M is Ti, Zr or Hf; Each X is F, Cl, Br, I, methyl, phenyl, benzyl, H, BH independently ₄, have 20 carbon atoms nearly-oxyl, have 20 carbon atoms nearly alkyl amino, there is nearly trialkyl silyl, the OBR' of 20 carbon atoms ₂---wherein R ' has to reach the alkyl of 12 carbon atoms or have nearly aryl or the SO of 12 carbon atoms ₃r "---wherein R " can be to have to reach the alkyl of 12 carbon atoms or there is the nearly aryl of 12 carbon atoms; Y is CR2, SiR ₂or R ₂cCR ₂group, it can be straight chain or have ring, and wherein R is hydrogen or alkyl; Cp ^a, Cp ^b, Cp ^cand Cp ^dto replace or unsubstituted ring pentadienyl, indenyl or fluorenyl independently of one another, and Cp wherein ^a, Cp ^b, Cp ^cand Cp ^don any substituting group can be H, there is the alkyl of 18 carbon atoms nearly or there is the nearly alkyl silyl of 18 carbon atoms.E represents bridged group, and it can comprise that (i) has nearly having of 18 carbon atoms and encircle or heterocyclic moiety; (ii) by general formula E ^ar ^3Ar ^4Athe group representing, wherein E ^ac, Si, Ge or B, and R ^3Aand R ^4Abe H independently or there is the nearly alkyl of 18 carbon atoms; (iii) by general formula-CR ^3Br ^4B-CR ^3Cr ^4Cthe group of-expression, wherein R ^3B, R ^4B, R ^3Cand R ^4Cbe H independently or there is the nearly alkyl of 10 carbon atoms; Or (iv) by general formula SiR ₂-CR ₂the group representing, wherein X is Si or C, and R is hydrogen or alkyl; Or-SiR ^3Dr ^4D-SiR ^3Er ^4E-, wherein R ^3D, R ^4D, R ^3Eand R ^4Ebe H independently or there is the nearly alkyl of 10 carbon atoms, and R wherein ^3A, R ^3B, R ^4A, R ^4B, R ^3C, R ^4C, R ^3D, R ^4D, R ^3E, R ^4Eor Cp, Cp ₁or at least one in substituting group on Cp2 is that (1) has the nearly end thiazolinyl of 12 carbon atoms; Or (2) binuclear compound, wherein each metal part has the constitutional features identical with MTE-B.Be applicable in the disclosure to be represented by structure (14)-(29) as the limiting examples of the compound of MTE-B:

In embodiment, CATCOMP further comprises chemically treated soild oxide, and it can serve as activator carrier.Alternatively, chemically treated soild oxide can comprise clay mineral, pillared clays, the clay that comes off, gelling be to the clay that comes off, layer silicate mineral, non-layer silicate mineral, lamellar aluminosilicate mineral, non-lamellar aluminosilicate mineral or its arbitrary combination in another matrix of oxide.

Generally, chemically treated soild oxide with corresponding untreated soild oxide Compound Phase than the acidity that presents enhancing.Chemically treated soild oxide also serves as catalyst activator compared with corresponding untreated soild oxide.Although chemically treated soild oxide activates transition metal salt complex in the non-existent situation of promotor, promotor also can be included in catalyst composition.Compared with comprising the catalyst composition of corresponding untreated soild oxide, the mobilizing function of activator carrier is being obvious aspect the increased activity of catalyst composition entirety.But, it is believed that chemically treated soild oxide can serve as activator, even in the non-existent situations such as the ionic compound of organo-aluminium compound, aikyiaiurnirsoxan beta, organic boron or organic boronic salt compound, ionization.

Chemically treated soild oxide can comprise the soild oxide by electrophilic anionic treatments.Although be not intended to be subject to following statement to retrain, it is believed that processing soild oxide by electrophilic component increases or strengthen the acidity of oxide compound.Therefore the Lewis that, activator carrier presents or acidity-as be greater than untreated soild oxide Lewis or strength of acid, or the acid sites quantity of activator carrier is greater than untreated soild oxide, or the two haves both at the same time.-kind quantitative chemical processing and the method for acidity untreated solid oxide material be by relatively process with the polymerization activity of untreated oxide compound under acid catalyzed reaction.

Chemically treated soild oxide of the present disclosure conventionally by present Lewis acid or acid behavior and have relatively much higher permeability inoganic solids oxide compound form.The chemical treatment that---is generally electrophilic negatively charged ion---of soild oxide electrophilic component, to form activator carrier.

According to the disclosure on the one hand, be greater than about 0.1cc/g for the preparation of the pore volume of the soild oxide of chemically treated soild oxide.According to the disclosure on the other hand, the pore volume of soild oxide is greater than about 0.5cc/g.According to the disclosure more on the one hand, the pore volume of soild oxide is greater than about 1.0cc/g.

On the other hand, the surface-area of soild oxide is about 100m ²/ g is to about 1000m ²/ g.Also on the one hand, the surface-area of soild oxide is about 200m ²/ g is to about 800m ²/ g.Again on the one hand, the surface-area of soild oxide is about 250m to the disclosure ²/ g is to about 600m ²/ g.

Chemically treated soild oxide can comprise such solid inorganic oxide: described solid inorganic oxide comprises that oxygen and one or more are selected from following element: periodictable the 2nd, 3,4,5,6,7,8,9,10,11,12,13,14 or 15 families; Or comprise that oxygen and one or more are selected from following element: lanthanon or actinide elements (referring to: Hawley's Condensed Chemical Dictionary, 1lth Ed., John Wiley & Sons, 1995; Cotton, F.A., Wilkinson, G., Murillo, C.A., and Bochmann, M., Advanced InorganicChemistry, 6th Ed., Wiley-Interscience, 1999).For example, inorganic oxide can comprise that oxygen and one or more are selected from following element: Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, TH, Ti, V, W, P, Y, Zn and Zr.

Can be used for forming the solid oxide material of chemically treated soild oxide or the suitable example of compound includes but not limited to Al ₂o ₃, B ₂o ₃, BeO, Bi ₂o ₃, CdO, Co ₃o ₄, Cr ₂o ₃, CuO, Fe ₂o ₃, Ga ₂o ₃, La ₂o ₃, Mn ₂o ₃, MoO ₃, NiO, P ₂o ₅, 86 ₂o ₅, SiO ₂, 8nO ₂, SrO, ThO ₂, TiO ₂, V ₂o ₅, WO ₃, Y ₂o ₃, ZnO, ZrO ₂deng, comprise its mixed oxide and combination thereof.For example, soild oxide can comprise aluminum oxide, aluminum phosphate, aluminophosphates, assorted poly-tungstate (heteropolytungstate), titanium dioxide, zirconium white, magnesium oxide, boron oxide, zinc oxide, its mixed oxide or its arbitrary combination of silicon-dioxide, aluminum oxide, silica-alumina, silicon-dioxide-coating.

Soild oxide of the present disclosure comprises that oxide material is if aluminum oxide, its " mixed oxide " compound are as silicon-dioxide _-aluminum oxide and combination thereof and mixture.Mixed oxidization compounds, if silica-alumina can be single chemofacies or many chemofaciess, wherein, more than a kind of metal and oxygen combination, forms solid oxidation compounds.The mixed oxide example that can be used for activator carrier of the present disclosure includes but not limited to silica-alumina, silica-titania, silicon-dioxide-zirconium white, zeolite, various clay mineral, aluminum oxide-titanium dioxide, aluminium oxide-zirconium oxide, Zinc aluminate, aluminum oxide-boron oxide, silicon-dioxide-boron oxide, aluminophosphates-silicon-dioxide, titanium dioxide titania-zirconia etc.Soild oxide of the present disclosure also comprises the aluminum oxide of oxide material such as silicon-dioxide-coating, and as United States Patent (USP) the 7th, described in 884, No. 163, its whole disclosures are incorporated to herein by reference.

For the treatment of the electrophilic component of soild oxide can be after processing with not with increase compared with the soild oxide of at least one electrophilic anionic treatments soild oxide Lewis or any component of acidity.According to the disclosure on the one hand, electrophilic component is as the electrophilic negatively charged ion of volatile organic compounds derived from the salt, acid or other compound that serve as this negatively charged ion source or precursor.The example of electrophilic negatively charged ion includes but not limited to sulfate radical, bisulfate ion, fluorine root, chlorine root, bromine root, iodine root, fluorosulfuric acid root, fluoroboric acid root, phosphate radical, hexafluorophosphoric acid root, trifluoroacetic acid root, trifluoromethanesulfonic acid root, fluorine zirconate, hydrofluotitanic acid root, phospho-wolframic acid root etc., comprises its mixture and combination.In addition other ion or the non-ionic compound that, serve as these electrophilic negatively charged ion source also can be used in the disclosure.In the disclosure is aspect some, consider that electrophilic negatively charged ion can be maybe to comprise fluorine root, chlorine root, bromine root, phosphate radical, trifluoromethanesulfonic acid root, bisulfate ion or sulfate radical etc. or its arbitrary combination.In other side, electrophilic negatively charged ion can comprise sulfate radical, bisulfate ion, fluorine root, chlorine root, bromine root, iodine root, fluorosulfuric acid root, fluoroboric acid root, phosphate radical, hexafluorophosphoric acid root, trifluoroacetic acid root, trifluoromethanesulfonic acid root, fluorine zirconate, hydrofluotitanic acid root etc. or its arbitrary combination.

Therefore, for example, the activator carrier using in catalyst composition (for example, chemically treated soild oxide) can be maybe to comprise fluorided alumina, chlorinated aluminas, bromination aluminum oxide, sulfated alumina, fluorinated silica-aluminum oxide, chlorodioxin SiClx-aluminum oxide, bromination silica-alumina, sulfation silica-alumina, fluorinated silica-zirconium white, chlorodioxin SiClx-zirconium white, bromination silicon-dioxide-zirconium white, sulfation silicon-dioxide-zirconium white, fluorinated silica-titanium dioxide, the aluminum oxide of fluorinated silica-coating, the aluminum oxide of sulfation silicon-dioxide-coating, the aluminum oxide of phosphorylation silicon-dioxide-coating etc. or its combination.On the one hand, activator carrier can be the aluminum oxide that maybe can comprise fluorided alumina, sulfated alumina, fluorinated silica-aluminum oxide, sulfation silica-alumina, fluorinated silica-coating, aluminum oxide, the aluminum oxide of phosphorylation silicon-dioxide-coating etc. or its arbitrary combination of sulfation silicon-dioxide-coating.On the other hand, activator carrier comprises fluorided alumina; Alternatively, comprise chlorinated aluminas; Alternatively, comprise sulfated alumina; Alternatively, comprise fluorinated silica-aluminum oxide; Alternatively, comprise sulfation silica-alumina; Alternatively, comprise fluorinated silica-zirconium white; Alternatively, comprise chlorodioxin SiClx-zirconium white; Or alternatively, comprise the aluminum oxide of fluorinated silica-coating.

In the time that electrophilic component comprises the salt of electrophilic negatively charged ion, in the optional comfortable calcination process of the gegenion of this salt or positively charged ion, make salt recover or resolve into any positively charged ion of acid.Determine that factor that concrete salt serves as the suitability in electrophilic negatively charged ion source includes but not limited to solubleness, the water absorbability of without ion pairing effect positively charged ion adverse effect, positively charged ion and negatively charged ion between, positively charged ion giving salt etc. of salt in expection solvent and the thermostability of negatively charged ion.Suitable cationic example in electrophilic anion salt includes but not limited to ammonium, trialkyl ammonium, tetra-allkylammonium, Si Wan Ji Phosphonium, H ⁺, [H (OEt ₂) 2] ⁺deng.

Further, one or more different electrophilic negatively charged ion combinations in varing proportions can be used for making the concrete acidity of activator carrier to be adjusted to expection level.The combination of electrophilic component can contact with oxide material simultaneously or separately and with the random order that the chemically treated soild oxide acidity of expection is provided.For example, the disclosure is to apply two or more electrophilic negatively charged ion with two or more independent contact procedures to carry out source compound on the one hand.

Therefore, an example of the method for the chemically treated soild oxide of this preparation is as follows: make soild oxide or soild oxide combination contact the first electrophilic negatively charged ion selected carry out source compound, to form the first mixture; By this first mixture calcining, then contact the second electrophilic negatively charged ion and carry out source compound, to form the second mixture; Then by the second mixture calcining, with the soild oxide of formation processing.In this method, it can be identical or different compound that the first and second electrophilic negatively charged ion carry out source compound.

According to the disclosure on the other hand, chemically treated soild oxide comprise with the processing of electrophilic component chemical and optionally use the metal source combination of solid inorganic oxide material, mixed oxide material or the inorganic oxide material of processing that---comprises metal-salt, metal ion or other metal-containing compound---.The limiting examples of metal or metal ion comprises zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium etc. or its combination.The example of the chemically treated soild oxide that comprises metal or metal ion includes but not limited to the aluminum oxide of burnettize, the aluminum oxide of titanium fluoride dipping, the aluminum oxide of zinc fluoride dipping, the silica-alumina of burnettize, the silica-alumina of zinc fluoride dipping, the aluminum oxide of sulfation zinc dipping, chlorination Zinc aluminate, fluoridize Zinc aluminate, sulfation Zinc aluminate, with the aluminum oxide of the acid-treated silicon-dioxide-coating of hexafluoro titanium, process aluminum oxide of the silicon-dioxide-coating of then fluoridizing etc. or its arbitrary combination with zinc.

Can apply any method with metal impregnation solid oxide material.It is first-class that the method in oxide compound contacting metal source---being generally salt or metal-containing compound---can include but not limited to gelling, gelling altogether, a kind of compound is impregnated into another kind of compound.As needs, metal-containing compound is added with solution form or is impregnated in soild oxide, with after change into load type metal through calcining.Therefore, solid inorganic oxide can further comprise and is selected from the metal of zinc, titanium, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum etc. or the combination of these metals.For example, zinc is generally used for flooding soild oxide, because it can low cost provides the catalyst activity of raising.

Can be before with electrophilic anionic treatments soild oxide, process soild oxide with metal-salt or metal-containing compound afterwards or simultaneously.After any contact method, the contact mixture of general calcining solid compound, electrophilic negatively charged ion and metal ion.Alternatively, contact and calcining solid oxide material, electrophilic negatively charged ion source and metal-salt or metal-containing compound carry out simultaneously.

Different methods is used to form and can be used for chemically treated soild oxide of the present disclosure.Chemically treated soild oxide can comprise the product of contact in one or more soild oxides and one or more electrophilic negatively charged ion source.Without calcining solid oxide compound before contact electrophilic negatively charged ion source.Generally during soild oxide contact electrophilic negatively charged ion source or calcine afterwards product of contact.Soild oxide can be through calcining or without calcining.Can be used for the several different methods of preparing soild oxide activator carrier of the present disclosure is in the news.For example, these methods are described in U.S. Patent number 6,107,230; 6,165,929; 6,294,494; 6,300,271; 6,316,553; 6,355,594; 6,376,415; 6,388,017; 6,391,816; 6,395,666; 6,524,987; 6,548,441; 6,548,442; 6,576,583; 6,613,712; 6,632,894; 6,667,274; With 6,750, in 302; These disclosed full contents are incorporated to herein by reference.

According to the disclosure on the one hand, solid oxide material is by carrying out as follows chemical treatment: making its contact electrophilic component, is generally electrophilic negatively charged ion source.Further, solid oxide material is optionally used metal ion chemical treatment, and then calcining, to form the chemically treated soild oxide of containing metal or metal impregnation.According to the disclosure on the other hand, carry out simultaneously in contact and calcining solid oxide material and electrophilic negatively charged ion source.

It is first-class to make that the method that oxide compound contact electrophilic component---is generally salt or the acid of electrophilic negatively charged ion---can include but not limited to gelling, gelling altogether, a kind of compound is impregnated into another kind of compound.Therefore, after any contact method, the contact mixture of calcining solid oxide compound, electrophilic negatively charged ion and optional metal ion.

Soild oxide activator carrier (, chemically treated soild oxide) therefore can be produced by the following method, comprising:

1) make soild oxide (one or more) contact electrophilic negatively charged ion carry out source compound (one or more), to form the first mixture; With

2) calcining the first mixture, to form soild oxide activator carrier.

According to the disclosure on the other hand, soild oxide activator carrier (chemically treated soild oxide) is produced by the following method, comprising:

1) make soild oxide (one or more) contact the first electrophilic negatively charged ion carry out source compound, to form the first mixture;

2) calcining the first mixture, to generate the first mixture of calcining;

3) make the first mixture of calcining contact the second electrophilic negatively charged ion and carry out source compound, to form the second mixture; With

4) calcining the second mixture, to form soild oxide activator carrier.

According to the another aspect of the disclosure, by following production or form chemically treated soild oxide: make soild oxide contact electrophilic negatively charged ion carry out source compound, wherein solid oxidation compounds before contact electrophilic negatively charged ion source, during or calcined afterwards, and wherein substantially there is not aikyiaiurnirsoxan beta, the ionic compound of organic boron or organic boronic salt compound and ionization.

The calcining of soild oxide of processing is carried out generally as follows: in ambiance, general in dry ambiance, at the temperature of approximately 200 DEG C to approximately 900 DEG C, and carry out time of approximately 1 minute to approximately 100 hours.Calcining can be carried out at the temperature of approximately 300 DEG C to approximately 800 DEG C or alternatively at the temperature of approximately 400 DEG C to approximately 700 DEG C.Calcining can be carried out approximately 30 minutes to approximately 50 hours or approximately 1 hour to approximately 15 hours.Therefore, for example, calcining can be implemented approximately 1 to approximately 10 hour at the temperature of approximately 350 DEG C to approximately 550 DEG C.Suitable ambiance can be applied in calcination process arbitrarily.Generally, calcining is carried out in as air in oxidizing atmosphere.Alternatively, can apply inert atmosphere, as nitrogen or argon gas; Or reducing atmosphere, as hydrogen or carbon monoxide.

According to the disclosure on the one hand, for solid oxide material, process in the source of halide ion, sulfate ion or negatively charged ion combination, optionally uses metal ion treatment, and then calcining, to provide the chemically treated soild oxide of solid particulate form.For example, solid oxide material can be originated with sulfate radical (being called as " sulfating agent "), chlorine root origin (being called as " chlorizating agent "), fluorine root origin (being called as " fluorizating agent ") or its combined treatment, and calcining, so that soild oxide activator to be provided.Available acidic activated agent carrier includes but not limited to bromination aluminum oxide, chlorinated aluminas, fluorided alumina, sulfated alumina, bromination silica-alumina, chlorodioxin SiClx-aluminum oxide, fluorinated silica-aluminum oxide, sulfation silica-alumina, bromination silicon-dioxide-zirconium white, chlorodioxin SiClx-zirconium white, fluorinated silica-zirconium white, sulfation silicon-dioxide-zirconium white, fluorinated silica-titanium dioxide, with the acid-treated aluminum oxide of hexafluoro titanium, with the aluminum oxide of the acid-treated silicon-dioxide-coating of hexafluoro titanium, with the silica-alumina of hexafluoro zirconate processing, with the silica-alumina of trifluoroacetic acid processing, fluorinated boron-aluminum oxide, with the silicon-dioxide of Tetrafluoroboric acid processing, with the aluminum oxide of Tetrafluoroboric acid processing, with the aluminum oxide of phosphofluoric acid processing, pillared clays is as column montmorillonite---optionally use fluorine root, chlorine root or sulfate radical processing, phosphorylation aluminum oxide or other aluminophosphates---optionally use sulfate radical, fluorion or chlorion processing, or above arbitrary combination.Enter-walk, optionally available metal ion processing of any in these activator carriers.

Chemically treated soild oxide can comprise the fluorinated solid oxide compound of solid particulate form.Fluorinated solid oxide compound can be by forming soild oxide contact fluorizating agent.Can be by as follows fluorine radical ion being added in oxide compound: form oxide compound at appropriate solvent as the slurries in alcohol or water, this solvent includes but not limited to 1 to 3 carbon alcohol---because its volatility and low surface tension.The example of suitable fluorizating agent includes but not limited to hydrofluoric acid (HF), Neutral ammonium fluoride (NH ₄f), ammonium bifluoride (NH ₄hF ₂), ammonium tetrafluoroborate (NH ₄bF ₄), silicofluoric acid (hexafluorosilicic acid) ammonium ((NH ₄) ₂siF ₆), ammonium hexafluorophosphate (NH ₄pF ₆), hexafluoro metatitanic acid (H ₂tiF ₆), ammonium hexa-fluorotitanate ((NH ₄) 2TiF ₆), hexafluoro zirconate (H ₂zrF ₆), AlF ₃, NH ₄alF ₄, its analogue and combination thereof.Also can apply trifluoromethanesulfonic acid and trifluoromethanesulfacid acid ammonium.For example, ammonium bifluoride (NH ₄hF ₂) can be used as fluorizating agent, because it is easy to use and acquisition.

As needs, soild oxide is used to fluorizating agent processing in calcining step.Can apply the fluorizating agent that can fully contact arbitrarily soild oxide in calcining step.For example, except aforementioned those fluorizating agents, also can apply volatility organic fluorine agent.Disclosure this respect can with the example of volatility organic fluorine agent include but not limited to freonll-11, perflexane, perfluor benzene, fluoromethane, trifluoroethanol etc. and combination thereof.Calcining temperature generally must be enough high with decomposition compound and release fluorine root.Gaseous hydrogen fluoride (HF) or fluorine (F ₂) itself also can apply together with soild oxide, if calcining is fluoridized simultaneously.Also can apply silicon tetrafluoride (SiF ₄) and comprise tetrafluoroborate (BF ₄ ^-) compound.A kind of method that makes easily soild oxide contact fluorizating agent is fluorizating agent to be evaporated to the air-flow for fluidization soild oxide in calcination process.

Similarly, on the other hand, chemically treated soild oxide comprises the chlorination soild oxide of solid particulate form to the disclosure.Chlorination soild oxide is by forming soild oxide contact chlorizating agent.Chlorion can add in oxide compound by forming the slurries of oxide compound in appropriate solvent.Soild oxide can be used chlorizating agent processing in calcining step.Can apply any can serve as chlorine root origin and in calcining step the abundant chlorizating agent of catalytic oxidation thing, as SiCl ₄, SiMe ₂cl ₂, TiCl ₄, BCl ₃deng, comprise its mixture.Can apply volatility organochlorine agent.The example of suitable volatility organochlorine agent includes but not limited to some freonll-11, perna, methyl chloride, methylene dichloride, chloroform, tetracol phenixin, ethapon etc. or its arbitrary combination.Itself also can apply gaseous hydrogen chloride or chlorine in calcination process together with soild oxide.A kind of method that makes easily oxide compound contact chlorizating agent is chlorizating agent to be evaporated to the air-flow for fluidization soild oxide in calcination process.

The amount of fluorine radical ion or chlorion is as general as by weight approximately 1 to approximately 50% before calcining solid oxide compound, and wherein weight percent is the weight based on for example silica-alumina of soild oxide before calcining.According to the disclosure on the other hand, the amount of fluorine radical ion or chlorion is by weight approximately 1 to approximately 25% before calcining solid oxide compound, and according to the disclosure on the other hand, is by weight approximately 2 to approximately 20%.According to the another aspect of the disclosure, the amount of fluorine radical ion or chlorion is by weight approximately 4 to approximately 10% before calcining solid oxide compound.With after halogen root dipping, can by the dry halogenation oxide compound of any appropriate means, the method includes but not limited to, then evaporation of suction filtration, vacuum-drying, spraying are dried etc., although also can start immediately calcining step, and the soild oxide of moist dipping.

The pore volume of silica-alumina for the preparation of the silica-alumina of processing is generally greater than about 0.5cc/g.According to the disclosure on the one hand, pore volume is greater than about 0.8cc/g, and according to the disclosure on the other hand, is greater than about 1.0cc/g.Further, the surface-area of silica-alumina is greater than about 100m generally ²/ g.According to the disclosure on the other hand, surface-area is greater than about 250m ²/ g.On the one hand, surface-area is greater than about 350m again ²/ g.

Be generally by weight approximately 5 to approximately 95% for the alumina content of silica-alumina of the present disclosure.According to the disclosure on the one hand, the alumina content of silica-alumina is by weight approximately 5 to approximately 50% or approximately 8% to approximately 30% aluminum oxide.On the other hand, can apply the silica-alumina compound of high alumina content, wherein the scope of the alumina content of these silica-alumina compounds is generally approximately 60% to approximately 90% or approximately 65% to approximately 80% aluminum oxide by weight.According to the another aspect of the disclosure, soild oxide component comprises aluminum oxide, and without silicon-dioxide, and according to the disclosure on the other hand, soild oxide component comprises silicon-dioxide, and alumina-free.

Sulfation soild oxide comprises the soild oxide component of sulfate radical and solid particulate form, as aluminum oxide or silica-alumina.Optionally, sulfation oxide compound is further used metal ion treatment, makes the sulfation oxide compound after calcining comprise metal.According to the disclosure on the one hand, sulfation soild oxide comprises sulfate radical and aluminum oxide.In some instances, sulfated alumina forms by the following method, and wherein aluminum oxide is originated for example sulfuric acid or vitriol as ammonium sulfate processing with sulfate radical.This method is undertaken by forming the slurries of aluminum oxide in appropriate solvent generally, and this solvent, as alcohol or water, has wherein added the sulfating agent of expection concentration.Suitable organic solvent includes but not limited to 1 to 3 carbon alcohol, because it has volatility and low surface tension.

According to the disclosure on the one hand, before calcining, the amount of sulfate ion is approximately 0.5 to approximately 100 weight part sulfate ion with respect to approximately 100 weight part soild oxides.According to the disclosure on the other hand, before calcining, the amount of sulfate ion is approximately 1 to approximately 50 weight part sulfate ion with respect to approximately 100 weight part soild oxides, with according to the disclosure more on the one hand, be approximately 5 to approximately 30 weight part sulfate ions with respect to approximately 100 weight part soild oxides.These weight ratios are the weight based on soild oxide before calcining.With after sulfate radical dipping, sulfation oxide compound can be dry by any appropriate means, includes but not limited to, then evaporation of suction filtration, vacuum-drying, spraying are dried etc., although also can start immediately calcining step.

According to the disclosure on the other hand, comprise ion-exchange type activator carrier for the preparation of the activator carrier of catalyst composition of the present disclosure, include but not limited to have silicate and silico-aluminate compound or the mineral of stratiform or non-laminate structure, and combination.The disclosure on the other hand in, ion-exchange type lamellar aluminosilicate is if pillared clays is as activator carrier.In the time that acidic activated agent carrier comprises ion-exchange type activator carrier, it is optionally by least one those electrophilic anionic treatments as disclosed herein, although general ion-exchange type activator carrier is without electrophilic anionic treatments.

According to the disclosure on the other hand, activator carrier of the present disclosure comprises the clay mineral of the layer that has crossover positively charged ion and can expand.General clay mineral activator carrier includes but not limited to that ion-exchange type lamellar aluminosilicate is as pillared clays.Although use term " carrier ", it does not mean the inert component that is construed to catalyst composition, but is construed as the active part of catalyst composition, because it has tight associated with transition metal salt complex component.

According to the disclosure on the other hand, clay material of the present disclosure comprises in native state or by the material of wetting, ion-exchange or post (pillaring) different ions processing.Generally, clay material activator carrier of the present disclosure comprises the clay that carries out ion-exchange with macrocation (comprising multinuclear, high electric charge metal complex positively charged ion).But, clay material activator carrier of the present disclosure also comprises the clay that carries out ion-exchange with simple salt, and this simple salt includes but not limited to that Al (III), Fe (II), Fe (III) and Zn (II) and part are as the salt of halogen root, acetate moiety, sulfate radical, nitrate radical or nitrite anions.

According to the disclosure on the other hand, activator carrier comprises pillared clays.Term " pillared clays " is for meaning and large-scale, general clay material multinuclear, that high electric charge metal complex positively charged ion carries out ion-exchange.The example of this ion includes but not limited to can have as 7 ⁺the Keggin ion, different multi-metal oxygen acid group and other large-scale ions of electric charge.Therefore the exchangeable cation that, term post means clay material is wherein reacted as the simple switched of Keggin ion substitution by large-scale highly charged ion.Then these polymerizing cationicallies are fixed in the middle layer of clay, and change into metal oxide " post " in the time of calcining, effectively support clay seam as post spline structure.Therefore,, once clay is dried and calcines to produce pillar stiffener between clay seam, the grid structure of expansion is kept and porousness is enhanced.The shape and size in the hole producing can change according to post formed material used and former clay material (parent clay material).The example of post and pillared clays is shown in: T.J.Pinnavaia, Science220 (4595), 365-371 (1983); J.M.Thomas, Intercalation Chemistry, (S.Whittington and A.Jacobson, eds.) Ch.3, pp.55-99, Academic Press, Inc., (1972); United States Patent (USP) the 4th, 452,910; 5,376,611; With 4,060, in No. 480; Its disclosure is all incorporated to herein by reference.

The utilization of post method has the clay mineral of exchangeable cation and the layer that can expand.Can apply the pillared clays of any polymerization that strengthens the alkene in disclosure catalyst composition.Therefore the clay mineral that, is suitable for post includes but not limited to malthacite; Smectite---dioctahedron (Al) and trioctahedron (Mg) and derivative thereof are as montmorillonite (wilkinite), nontronite, hectorite or hectorite (laponites); Halloysite; Vermiculite; Mica; Fluorine mica; Chlorite; Mixed layer clay; Fiber clay, includes but not limited to sepiolite, attapulgite and polygorskite; Serpentine clay; Illite; Hectorite; Saponite; And arbitrary combination.On the one hand, pillared clays activator carrier comprises wilkinite or montmorillonite.Bentonitic main ingredient is montmorillonite.

As needs, pillared clays can be pretreated.For example, column wilkinite by approximately 300 DEG C, within approximately 3 hours, carry out pre-treatment inert atmosphere (being generally dry nitrogen) is lower dry, then add polymerization reactor.Although this paper describes exemplary pre-treatment, should understand preheating and can carry out by multiple other temperature and time, comprise the arbitrary combination of temperature and time step, it is all comprised by the disclosure.

For the preparation of activator carrier other inorganic carrier material capable of being combined of catalyst composition of the present disclosure, include but not limited to zeolite, inorganic oxide, phosphorylation inorganic oxide etc.On the one hand, general solid support material used includes but not limited to silicon-dioxide, silica-alumina, aluminum oxide, titanium dioxide, zirconium white, magnesium oxide, boron oxide, Thorotrast, aluminophosphates, aluminum phosphate, silica-titania, co-precipitation earth silicon/titanic oxide, its mixture or its arbitrary combination.In embodiment, activator carrier comprises sulfation soild oxide activator carrier (SSA).

The method of preparing these activator carriers can comprise that precipitation, co-precipitation, dipping, gelation, hole-gelation, calcining (nearly at 900 DEG C), spraying are dry, rapid drying (flash-drying), Rotary drying and calcining, grinding, screening and similar operations.

In embodiment, CATCOMP optionally comprises metal alkyl or the metalloid alkyl that can serve as promotor.Generally, the metal alkyl compound that can be used for catalyst system of the present disclosure can be assortedly arbitrarily to join or all join metal alkyl compound.In embodiment, that metal alkyl can comprise is following, mainly by forming below or by forming below: non-halogen root metal alkyl, metal halide alkyl or its arbitrary combination; Alternatively, non-halogen root metal alkyl; Or alternatively, metal halide alkyl.

In embodiment, that the metal of metal alkyl can comprise is following, mainly by forming below or by forming below: 1st, 2,11,12,13 or 14 family's metals; Or alternatively, the 13rd or 14 family's metals; Or alternatively, the 13rd family's metal.In some embodiments, the metal of metal alkyl (non-halogen root metal alkyl or metal halide alkyl) can be lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, boron, aluminium or tin; Alternatively, lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminium or tin; Alternatively, lithium, sodium or potassium; Alternatively, magnesium, calcium; Alternatively, lithium; Alternatively, sodium; Alternatively, potassium; Alternatively, magnesium; Alternatively, calcium; Alternatively, zinc; Alternatively, boron; Alternatively, aluminium; Or alternatively, tin.In some embodiments, metal alkyl (non-halogen root metal alkyl or metal halide alkyl) can comprise following, mainly by forming below or by forming below: lithium alkyl, sodium alkyl, magnane base, boryl, zinc alkyl or aluminium alkyl.In some embodiments, metal alkyl (non-halogen root metal alkyl or metal halide alkyl) can comprise following, mainly by forming below or by forming below: aluminium alkyl.

In embodiment, aluminium alkyl can be trialkylaluminium, alkyl aluminum halide, alkoxide aluminum alkyls, aikyiaiurnirsoxan beta or its arbitrary combination.In some embodiments, aluminium alkyl can be trialkylaluminium, alkyl aluminum halide, aikyiaiurnirsoxan beta or its arbitrary combination; Or alternatively, trialkylaluminium, aikyiaiurnirsoxan beta or its arbitrary combination.In other embodiments, aluminium alkyl can be trialkylaluminium; Alternatively, alkyl aluminum halide; Alternatively, alkoxide aluminum alkyls; Or alternatively, aikyiaiurnirsoxan beta.

In non-limiting embodiment, aikyiaiurnirsoxan beta can have repeating unit, it is characterized in that formula I:

Wherein R ' is straight or branched alkyl.The alkyl of metal alkyl is described in this article, and can be ad lib for further describing the aikyiaiurnirsoxan beta with formula I.Generally, the n of formula I is greater than 1; Or alternatively, be greater than 2.In embodiment, the scope of n can be 2 to 15; Or alternatively, in 3 to 10 scope.

On the one hand, each halogen root of any metal halide alkyl disclosed herein can be fluorine root, chlorine root, bromine root or iodine root independently; Alternatively, chlorine root, bromine root or iodine root.In embodiment, each halogen root of any metal halide alkyl disclosed herein can be fluorine root; Alternatively, chlorine root; Alternatively, bromine root; Or alternatively, iodine root.

On the one hand, the alkyl of any metal alkyl disclosed herein (non-halogen root metal alkyl or metal halide alkyl) can be C independently of one another ₁to C ₂₀alkyl; Alternatively, C ₁to C10 alkyl; Or alternatively, C ₁to C ₆alkyl.In embodiment, alkyl (one or more) can be methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or octyl group independently of one another; Alternatively, methyl, ethyl, butyl, hexyl or octyl group.In some embodiments, alkyl can be methyl, ethyl, n-propyl, normal-butyl, isobutyl-, n-hexyl or n-octyl independently of one another; Alternatively, methyl, ethyl, normal-butyl or isobutyl-; Alternatively, methyl; Alternatively, ethyl; Alternatively, n-propyl; Alternatively, normal-butyl; Alternatively, isobutyl-; Alternatively, n-hexyl; Or alternatively, n-octyl.

On the one hand, the alkoxyl group of any alkoxide metal alkyl disclosed herein can be C independently of one another ₁to C ₂₀alkoxyl group; Alternatively, C ₁to C ₁₀alkoxyl group; Or alternatively, C ₁to C ₆alkoxyl group.In embodiment, each alkoxyl group of any alkoxide metal alkyl disclosed herein can be independently of one another methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy, hexyloxy, heptan oxygen base or octyloxy; Alternatively, methoxyl group, oxyethyl group, butoxy, hexyloxy or octyloxy.In some embodiments, each alkoxyl group of any alkoxide metal alkyl disclosed herein can be methoxyl group, oxyethyl group, positive propoxy, n-butoxy, isobutoxy, positive hexyloxy or n-octyloxy independently of one another; Alternatively, methoxyl group, oxyethyl group, n-butoxy or isobutoxy; Alternatively, methoxyl group; Alternatively, oxyethyl group; Alternatively, positive propoxy; Alternatively, n-butoxy; Alternatively, isobutoxy; Alternatively, positive hexyloxy; Or alternatively, n-octyloxy.

In non-limiting embodiment, available metal alkyl can comprise lithium methide, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, magnesium ethide, di-n-butyl magnesium, ethyl-magnesium-chloride, chlorination normal-butyl magnesium and zinc ethyl.

In non-limiting embodiment, available trialkyl aluminium compound can comprise trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, three hexyl aluminium, trioctylaluminum or its mixture.In some non-limiting embodiments, trialkyl aluminium compound can comprise trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, three hexyl aluminium, tri-n-octylaluminium or its mixture; Alternatively, triethyl aluminum, three n-butylaluminum, triisobutyl aluminium, three hexyl aluminium, tri-n-octylaluminium or its mixture; Alternatively, triethyl aluminum, three n-butylaluminum, three hexyl aluminium, tri-n-octylaluminium or its mixture.In other non-limiting embodiment, available trialkyl aluminium compound can comprise trimethyl aluminium; Alternatively, triethyl aluminum; Alternatively, tri-propyl aluminum; Alternatively, three n-butylaluminum; Alternatively, triisobutyl aluminium; Alternatively, three hexyl aluminium; Or alternatively, tri-n-octylaluminium.

In non-limiting embodiment, available alkyl aluminum halide can comprise diethylaluminum chloride, bromination diethyl aluminum, ethylaluminium dichloride, sesquialter ethylaluminium chloride and composition thereof.In some non-limiting embodiments, available alkyl aluminum halide can comprise diethylaluminum chloride, ethylaluminium dichloride, sesquialter ethylaluminium chloride and composition thereof.In other non-limiting embodiment, available alkyl aluminum halide can comprise diethylaluminum chloride; Alternatively, bromination diethyl aluminum; Alternatively, ethylaluminium dichloride; Or alternatively, sesquialter ethylaluminium chloride.

In non-limiting embodiment, available aikyiaiurnirsoxan beta can comprise methylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane (MMAO), n-propyl aikyiaiurnirsoxan beta, sec.-propyl aikyiaiurnirsoxan beta, normal-butyl alumina alkane, sec-butyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide, tertiary butyl aikyiaiurnirsoxan beta, 1-amyl group aikyiaiurnirsoxan beta, 2-amyl group aikyiaiurnirsoxan beta, 3-amyl group aikyiaiurnirsoxan beta, isopentyl aikyiaiurnirsoxan beta, neo-pentyl aikyiaiurnirsoxan beta or its mixture; In some non-limiting embodiments, available aikyiaiurnirsoxan beta can comprise methylaluminoxane (MAO), modified methylaluminoxane (MMAO), isobutyl aluminium alkoxide, tertiary butyl aikyiaiurnirsoxan beta or its mixture.In other non-limiting embodiment, available aikyiaiurnirsoxan beta can comprise methylaluminoxane (MAO); Alternatively, ethylaluminoxane; Alternatively, modified methylaluminoxane (MMAO); Alternatively, n-propyl aikyiaiurnirsoxan beta; Alternatively, sec.-propyl aikyiaiurnirsoxan beta; Alternatively, normal-butyl alumina alkane; Alternatively, sec-butyl aikyiaiurnirsoxan beta; Alternatively, isobutyl aluminium alkoxide; Alternatively, tertiary butyl aikyiaiurnirsoxan beta; Alternatively, 1-amyl group aikyiaiurnirsoxan beta; Alternatively, 2-amyl group aikyiaiurnirsoxan beta; Alternatively, 3-amyl group aikyiaiurnirsoxan beta; Alternatively, isopentyl aikyiaiurnirsoxan beta; Or alternatively, neo-pentyl aikyiaiurnirsoxan beta.

In embodiment, metal alkyl comprises organoboron compound or organic boronic salt compound.Organic boron or organic boronic salt compound comprise neutral boron compound, borate etc. or its combination.For example, consider fluorine organoboron compound and fluorine organic boronic salt compound.

For the disclosure, can utilize any fluorine organic boron or fluorine organic boronic salt compound.The example that can be used for fluorine organic boronic salt compound of the present disclosure includes but not limited to that fluoro aryl borate is as DMA four (pentafluorophenyl group) borate, triphenylcarbenium four (pentafluorophenyl group) borate, four (pentafluorophenyl group) lithium tetraborate, DMA four [3,5-bis-(trifluoromethyl) phenyl] borate, triphenylcarbenium four [3,5-bis-(trifluoromethyl) phenyl] borate etc. or its mixture.The example that can be used for fluorine organoboron compound of the present disclosure includes but not limited to three (pentafluorophenyl group) boron, three [3,5-bis-(trifluoromethyl) phenyl] boron etc. or its mixture.Although be not intended to be subject to following theory constraint, these examples of fluorine organic borate and fluorine organoboron compound and related compound are considered to form " weak coordination " negatively charged ion in the time of combination organometallic compound, as United States Patent (USP) the 5th, 919, No. 983 disclosed obtaining, its disclosure is all incorporated to herein by reference.Applicant also examines other dual-function compound that comprises two or more boron atoms in the two boron of application or two boron compounds or chemical structure, such as J.Am.Chem.Soc., 2005,127, disclosed in pp.14756-14768, its content is all incorporated to herein by reference.

On the one hand, the weight ratio of the soild oxide component of processing and CATCOMP (for example, imines phenolic compound and MTE-A or imines-phenolic compound and MTE-B) can be approximately 10, and 000:1 is to about 10:1.On the other hand, the soild oxide component of processing and the weight ratio of CATCOMP can be that about 5000:1 is to about 10:1; Also on the other hand, about 2000:1 to 50:1.These weight ratios are promotor (for example, organoaluminum, the oxide compound of processing) based on for the preparation of catalyst composition and the combination weight of CATCOMP, and with the sequence independence of contact catalyst component.In embodiment, the gross weight of the ratio that the metal salt complex of imines phenolic compound and metallocene exist in CATCOMP based on CATCOMP is that about 100:1 is to about 1:100, about 20:1 is to about 1:20 alternatively, or alternatively about 10:1 to about 1:10.

In embodiment, the scope that openly CATCOMP of type presents polyreaction catalytic activity is herein that about 1g PE/g cath is to approximately 1,000,000kgPE/g cath, about 1kg PE/g cath is to approximately 100 alternatively, 000kgPE/g cath, or alternatively about 10kgPE/g cath to approximately 10,000kgPE/g cath.Catalyst system activity starts the product grams generating for 30 minutes through reacting while being defined as every gram of transition metal salt complex for catalyst system from whole catalyst system contact alkene.Catalyst system activity can be described with regard to the different products of olefin oligomerization or polymerization.

In embodiment, openly the catalyst system of type is used for utilizing dissimilar polymerization reactor to prepare polymkeric substance by any olefine polymerizing process herein.As used herein, " polymerization reactor " comprise can polymerization of olefin monomers to generate any reactor of homopolymer and/or multipolymer.The homopolymer generating in reactor and/or multipolymer can be called as resin and/or polymkeric substance.Dissimilar reactor include but not limited to following those, it can be called as intermittent type, slurries, gas phase, solution, high pressure, tubular type, autoclave or other a kind of and/or multiple reactor.Gas-phase reactor can comprise fluidized-bed reactor or multistage horizontal reactor.Slurry-phase reactor can comprise vertical and/or horizontal circuit.High-pressure reactor can comprise autoclave and/or tubular reactor.Type of reactor can comprise intermittently and/or successive processes.Successive processes can be applied batch-type and/or the discharge of successive type product or shift.Process also can comprise partially or completely directly other material of recirculation unreacted monomer, unreacted comonomer, catalyzer and/or promotor, thinner and/or polymerization process.Polymerization reactor system of the present disclosure can comprise in system the reactor of a type or the multiple reactors with the identical or different type of suitable arbitrarily configuration operation.Polymer production in multiple reactor can be included in the several stages at least two independent polymerization reactors, and this polymerization reactor interconnects by transfer system, and the polymkeric substance that the first polymerization reactor is produced can be transferred in the second reactor.Alternatively, the polymerization in multiple reactor can comprise that polymkeric substance shifts from a reactor---manually or automatically---to follow-up one or more reactors, to carry out other polymerization.Alternatively, multistage or multistep polymerization can occur in single reactor, wherein changes condition so that different polyreaction occurs.

The expection polymerizing condition of one of them reactor can be related with producing the whole process of polymkeric substance of the present disclosure the operational condition of any other reactor identical or different.Multiple reactor system can comprise arbitrary combination, include but not limited to the combination of the combination of multiple loop reactors, multiple Gas-phase reactor, loop reactor and Gas-phase reactor, multiple high-pressure reactor or high-pressure reactor and loop reactor and/or Gas-phase reactor.Multiple reactors can serial or parallel connection operation.In embodiment, arbitrary arrangement and/or arbitrary combination that can application response device be produced polymkeric substance of the present disclosure.

According to an embodiment, polymerization reactor system can comprise at least one loop slurry-phase reactor.This reactor can comprise horizontal or vertical loop.Monomer, thinner, catalyst system and optionally arbitrarily comonomer can be continuously supplied to the loop slurry-phase reactor that carries out polymerization.Generally, successive processes can comprise by monomer, catalyzer and/or thinner introduce continuously polymerization reactor and from then on reactor remove continuously the suspension that comprises polymer beads and thinner.Reactor effluent can be through flash distillation to remove the liquid comprising from the thinner of solid polymer, monomer and/or comonomer.Different technologies can be used for this separating step, includes but not limited to, and flash distillation, it can comprise the arbitrary combination of the gain of heat and decompression; In cyclonic separator or wet cyclone, separate by whirlwind effect; By centrifugation; Or other suitable separation method.

General slurry polymerization method (being also referred to as particle type method (particle-form processes)) is disclosed for example United States Patent (USP) the 3rd, 248,179,4,501,885,5,565,175,5,575,979,6,239,235,6,262,191 and 6, in 833, No. 415; Wherein each is all incorporated to herein by reference.

Include but not limited to the monomer of polymerization and under reaction conditions, be the hydrocarbon of liquid for the suitable thinner of slurry polymerization.The example of suitable thinner includes but not limited to hydrocarbon, as propane, hexanaphthene, Trimethylmethane, normal butane, Skellysolve A, iso-pentane, neopentane and Skellysolve A.Some loop polymerization reactions can be carried out under bulk conditions (bulk conditions), wherein do not use thinner.Example is the polymerization of propylene monomer, and as United States Patent (USP) the 5th, 455, No. 314 disclosed, and it is all incorporated to herein by reference.

According to an embodiment again, polymerization reactor can comprise at least one Gas-phase reactor.This system can be utilized the continuous recirculation flow that comprises one or more monomers by fluidized-bed continuous circulation under polymerizing condition, in the situation that catalyzer exists.Recirculation flow can be discharged also recirculation from fluidized-bed and be got back to reactor.Meanwhile, polymeric articles can be discharged from reactor, and monomer new or new system can be added into substitute the monomer of polymerization.This Gas-phase reactor can comprise alkene multistep gas-phase polymerization processes, and wherein alkene, at least two independently polymerizations in gas phase in vapour phase polymerization region, is supplied to second zone of convergency by the polymkeric substance that comprises catalyzer forming in first zone of convergency simultaneously.A kind of Gas-phase reactor is disclosed United States Patent (USP) the 4th, and 588,790,5,352,749, and in 5,436, No. 304, wherein each is all incorporated to herein by reference.

According to an embodiment again, pressure polymerization reactor can comprise tubular reactor or autoclave reactor.Tubular reactor can have some regions, wherein adds monomer, inhibitor or the catalyzer of new system.Monomer can be entrained in inert gas, and is introduced into a region of reactor.Inhibitor, catalyzer and/or catalyst component can be entrained in air-flow, and are introduced into another region of reactor.Air-flow can mix to carry out polymerization mutually.Suitably use heat and pressure are to obtain best polymeric reaction condition.

According to an embodiment again, polymerization reactor can comprise solution polymerization reactor, and wherein monomer is by suitable stirring or other means contact catalyst composition.Can apply the carrier that comprises organic thinner or excess monomer.As needs, fluent material exist or non-existent situation under, can make the monomer can vapor phase contact catalysis reaction product.The zone of convergency remains on the temperature and pressure that causes being formed on the polymers soln in reaction medium.Can apply and stir to obtain good temperature control in the whole zone of convergency and keep uniform polyblend.Suitably means are used for the polymerization exotherm that dissipates.

Be suitable for the arbitrary combination that polymerization reactor of the present disclosure can further comprise at least one Material supply system, at least one catalyzer or catalyst component supply system and/or at least one polymer recovery system.Appropriate reaction device system of the present invention can further comprise for feed purifying, catalyst stores and preparation, extrudes, the system of reactor cooling, polymer recovery, fractionation, recirculation, storage, shipment (loadout), lab analysis and process control.

For polymerization efficiency with provide condition that polymer property is controlled to include but not limited to the concentration of temperature, pressure, catalyzer or promotor type and quantity and differential responses thing.Polymerization temperature can affect catalyst productivity, polymericular weight and molecular weight distribution.Suitable polymerization temperature can be according to the arbitrary temp below the depolymerization temperature of Gibbs free energy equation.Generally, this comprises for example approximately 60 DEG C to approximately 280 DEG C, and/or approximately 70 DEG C to approximately 110 DEG C, depends on the type of polymerization reactor and/or polymerization process.

Suitable pressure also will change according to reactor and polymerization process.In loop reactor, the pressure of liquid polymerization is generally less than 1000psig.The pressure of vapour phase polymerization is conventionally at about 200-500psig.High pressure polymerisation in tubular type or autoclave reactor carries out approximately 20,000 to 75,000psig generally.In the supercritical region that polymerization reactor also can exist under common comparatively high temps and pressure, move.More than the stagnation point of Pressure/Temperature figure, the operation of (supercritical phase) can provide advantage.

The concentration of differential responses thing can be controlled to produce the polymkeric substance with specific Physical and mechanical properties of polyoropylene.The end-use product by polymer formation proposing can change with the method that forms this product, to determine the finished product character of expectation.Mechanical properties includes but not limited to tensile strength, modulus in flexure, shock resistance, creep, stress relaxation and hardness test.Physical properties includes but not limited to density, molecular weight, molecular weight distribution, melt temperature, second-order transition temperature, crystalline melt temperature (temperature melt of crystallization), density, taxis, crack growth, short-chain branched, long chain branching and rheology measurement.

The concentration of monomer, comonomer, hydrogen, promotor, properties-correcting agent and electron donor is important for producing concrete polymer property generally.Comonomer can be used for controlling product density.Hydrogen can be used for controlling molecular weight of product.Promotor can be used for alkylation, removes poisonous substance and/or controls molecular weight.Concentration of poisons can be minimized, because poisonous substance can affect reaction and/or otherwise affect polymer product character.Properties-correcting agent can be used for controlling product characteristics, and electron donor can affect taxis.

In embodiment, CATCOMP comprises imines phenolic compound, it is characterized in that structure XV; Metallocenic compound, is characterized in that structure 15 or structure 18; The sulfation soild oxide of type is disclosed herein; The aluminum alkyls complex compound of type is disclosed herein.

CATCOMP can for example, contact monomer (for example, ethene and optional comonomer) under the condition that is suitable for forming polymkeric substance (, polyethylene).In embodiment, utilize method polymerization single polymerization monomer disclosed herein (for example, ethene), generate polymkeric substance.Polymkeric substance can comprise homopolymer, multipolymer or its combination.In embodiment, polymkeric substance is multipolymer, and it comprises ethene and one or more comonomers, as for example, and alhpa olefin.The example of suitable comonomer includes but not limited to have the unsaturated hydrocarbons of 3 to 20 carbon atoms, as propylene, 1-butylene, 1-amylene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, and composition thereof.In embodiment, comonomer is 1-hexene.In embodiment, in polymkeric substance, the amount of comonomer can be equal to or less than about 0.5mol.%, is less than alternatively about 0.4mol.%, is less than alternatively about 0.3mol.%, or is less than alternatively about 0.2mol.%.In embodiment, polymkeric substance is homopolymer.The comonomer that is appreciated that trace (inconsequential amount) can be present in polymkeric substance disclosed herein, and this polymkeric substance is still considered to homopolymer.At this, the comonomer of trace means not affect in fact the amount of the character of polymkeric substance disclosed herein.

Polymkeric substance can comprise other additive.Example additives includes but not limited to static inhibitor, tinting material, stablizer, nucleator, surface-modifying agent, pigment, slip(ping)agent, antiblocking agent, tackifier, polymer processing aids and combination thereof.These additives can be applied alone or in combination, and can preparation polymkeric substance described herein before, during or be included in afterwards in polymkeric substance.These additives can add via arbitrarily suitable technology, for example, and during extruding or coordinating (compounding) step, as during granulating or subsequent disposal becomes end-use goods.

In embodiment, the polymkeric substance of type described herein is two-component system, comprises the first component, and it is named as component A; And second component, it is named as B component.Polymkeric substance can be apply herein type openly catalyst system (, imines (two) phenolic compound, metallocenes) form reactor blend, wherein polymkeric substance passes through polymerization single polymerization monomer (for example, the alkene) in the situation that of all types catalyst system disclosed herein and metal alkyl existence and forms.In embodiment, component A and B component have overlapping molecular weight distribution profile (profile), and the MWD profile of B component is comprised by the MWD profile of component A.Component A can have following polymkeric substance framework: it is characterized in that wide MWD, high-density and straight chain substantially.B component can have following polymkeric substance framework: it is characterized in that, compared with component A time, narrow MWD and branch increase.In these features, each is all described in more detail later.The amount of component A can account for approximately 1 weight percent (wt.%) to about 99wt.% based on total polymer weight, and about 10wt.% is to about 90wt.% alternatively, or alternatively about 20wt.% to about 80wt.%.In embodiment, being greater than of the rest part of polymkeric substance approximately 90%, 91,92,93,94,95,96,97,98 or 99% comprises B component.

In embodiment, component A is characterised in that density is about 0.94g/cc to about 0.98g/cc, and about 0.95g/cc is to about 0.980g/cc alternatively, or alternatively about 0.955g/cc to about 0.980g/cc, as measured according to ASTM D-1505.The feature of B component can be that density is about 0.86g/cc to about 0.98g/cc, and about 0.87g/cc is to about 0.97g/cc alternatively, or alternatively about 0.88g/cc to about 0.96g/cc, as measured according to ASTM D-1505.

In embodiment, the polymkeric substance of type described herein is multimodal.At this, " mode (modality) " of polymkeric substance refers to the form of its molecular weight distribution curve, i.e. apparent as the figure of the function of its molecular weight of polymer weight mark.Polymer weight mark means the weight fraction to the molecule of sizing.Molecular weight distribution curve shows that the polymkeric substance at single peak can be called as unimodal polymerisation thing, the polymkeric substance at two different peaks of curve display can be called as bimodal polymers, the polymkeric substance at three different peaks of curve display can be called as three peak polymkeric substance, the polymkeric substance at two or more peaks of curve display can be called as multimodal, etc.Polymkeric substance mode can apply any appropriate means determine, such as in this paper embodiment part, describe those.

In embodiment, weight-average molecular weight (Mw) scope of the component A of the polymkeric substance of type described herein can be that about 50kg/mol is to about 1000kg/mol, about 100kg/mol is to about 750kg/mol alternatively, or alternatively about 200kg/mol to about 500kg/mol, and the Mw scope of B component can be that about 20kg/mol is to about 2000kg/mol, about 50kg/mol is to about 1500kg/mol alternatively, or alternatively about 100kg/mol to about 1000kg/mol.The M of polymer composition entirety _wscope can be extremely about 1000kg/mol of about 50kg/mol, and about 75kg/mol is to about 750kg/mol alternatively, and about 100kg/mol is to about 500kg/mol alternatively.Weight-average molecular weight is described the molecular weight distribution of polymkeric substance, and calculates according to equation 1:

M_{w} = \frac{Σ_{i} N_{i} {M_{i}}^{2}}{Σ_{i} N_{i} M_{i}} - - - (1)

Wherein N _imolecular weight M _imolecular amounts.

The M of polymer composition entirety _nscope can be extremely about 100kg/mol of about 1kg/mol, and about 5kg/mol is to about 50kg/mol alternatively, and about 10kg/mol is to about 30kg/mol alternatively.Number-average molecular weight is the simple average value (common average) of each polymericular weight, and can calculate according to equation 2:

M_{n} = \frac{Σ_{i} N_{i} M_{i}}{Σ_{i} N_{i}} - - - (2)

Wherein N _imolecular weight M _imolecular amounts.

Openly the feature of the polymkeric substance of type can be peak molecular weight (M herein _p) be about 10kg/mol to about 1000kg/mol, about 50kg/mol is to about 500kg/mol alternatively, or alternatively about 50kg/mol to about 400kg/mol.M _pmean highest weight, and be the pattern of MWD.

In embodiment, the feature of the polymkeric substance of type described herein can be that the MWD of component A is greater than approximately 20, is greater than approximately 25 alternatively, or be greater than alternatively approximately 30, and the feature of B component can be that MWD is less than approximately 20, is less than alternatively approximately 15, be less than alternatively approximately 10, or be less than alternatively approximately 5.The feature of the polyalcohol integral of type described herein can be that MWD is approximately 3 to approximately 100, alternatively approximately 6 to approximately 75, or alternatively approximately 10 to approximately 50.MWD is M _wwith number-average molecular weight (M _n) ratio, it is also referred to as polydispersity index (PDI) or is called more simply polydispersity.

The feature of the polymkeric substance of type described herein can further be z average molecular weight (M _z) and M _wratio (M _z/ M _w) be approximately 1.5 to approximately 20, alternatively approximately 2 to approximately 15, or alternatively approximately 3 to approximately 10.Z average molecular weight is high-order (higherorder) molar mass average value, and it calculates according to equation 3:

M_{z} = \frac{Σ_{i} N_{i} {M_{i}}^{3}}{Σ_{i} N_{i} {M_{i}}^{2}} - - - (3)

Wherein N _ithe amount of substance of kind i, M _iit is the molecular weight of kind i.M _z/ M _wrepresent than the another kind that is polymer MW D width.

In embodiment, the polymkeric substance of type described herein can have high load melt index, HLMI, and its scope is that about 0.01g/10min. is to about 1000g/10min., alternatively about 0.1g/10min.To about 100g/10min., or alternatively about 1g/10min. to about 20g/10min.When high load melt index (HLMI) means to stand the power of 21,600 grams according to ASTM D1238 at 190 DEG C, polymkeric substance can be pushed through the speed of the squeezing rheometer mouth of 0.0824 inch diameter.

In embodiment, the Carreau Yasuda ' a ' parameter of the polymkeric substance of type openly herein, the scope of CY-a is approximately 0.05 to approximately 0.8, alternatively approximately 0.1 to approximately 0.5, or alternatively approximately 0.15 to approximately 0.4.Carreau Yasuda ' a ' parameter (CY-a) is defined as rheology width parameter.Rheology width means width of transition zone between newton and the power law type shearing rate of polymkeric substance or the frequency dependence of polymer viscosity.Rheology width is the function of the distribution of relaxation times of fluoropolymer resin, the distribution of relaxation times of fluoropolymer resin and then be the function of resinous molecular structure or framework.CY-a parameter can obtain by hypothesis CoX-Merz rule, and can be by calculating at the fitted flow discharge curve that utilizes generation in the linearity-visco-elasticity dynamic oscillation frequency sweeping experiment that improves Carreau-Yasuda (CY) model, it is represented by equation (4):

Wherein

E=viscosity (Pas)

A=rheology width parameter

T _ξ=the relaxation time (one or more) [describing the timi requirement (location) of zone of transition]

E _o=zero-shear viscosity (Pa.s) [limiting newton's platform (Newtonian plateau)]

N=power law constant [limiting the final slope in high shear rate district]

For contributing to model-fitting, power law constant n remains on steady state value.The meaning of CY model and derivative parameter and and explain details be found in: C.A.Hieber and H.H.Chiang, RheoL Acta, 28,321 (1989); C.A.Hieberand H.H.Chiang, Polym.Eng.Sci., 32,931 (1992); And R.B.Bird, R.C.Armstrong and O.Hasseger, Dynamics of Polymeric Liquids, Volume l, Fluid Mechan ⁱcs, 2nd Edition, in JohnWiley & Sons (1987), wherein each is all incorporated to herein by reference.

In embodiment, zero-shear viscosity (η of the polymkeric substance of type described herein ₀) can be about 1E+03Pa-s to about 1E+10Pa-s, about 1E+04Pa-s is to about 1E+09Pa-s alternatively, or alternatively about 1E+05Pa-s to about 1E+08Pa-s.

In embodiment, openly the polymkeric substance of type is further characterized in that the reverse comonomer branching distribution or the reverse short-chain branched distribution (SCBD) that cause short-chain branched (SCB) herein, and it mainly occurs in the B component of polymkeric substance.At this, SCBD means the SCB quantity of every 1000 carbon atoms under each MW of the MWD profile across (across) polymkeric substance.

In embodiment, openly the polymkeric substance of type is characterized in that short-chain branched content is for every approximately 0.1 to approximately 20 short chain branch of 1000 carbon atoms altogether herein, alternatively approximately 0.5 to approximately 15, or alternatively approximately 1 to approximately 10.In another embodiment, the short chain numbers of branches of the amount that openly polymkeric substance of type is characterised in that SCB in B component herein based on every 1000 carbon atoms accounts for approximately 75% to approximately 100%, short chain numbers of branches approximately 80% to approximately 100% based on every 1000 carbon atoms alternatively, alternatively the short chain numbers of branches approximately 90% to approximately 100% based on every 1000 carbon atoms.

In embodiment, openly the polymkeric substance of type is the reactor blend of polymkeric substance herein, and it makes imines (two) phenolic compound of all types disclosed herein, Metallocenic compound contact with monomer with metal alkyl and prepare under the condition that is suitable for forming polymkeric substance.In embodiment, monomer is ethene.Alternatively, the polymkeric substance of formation comprises ethene and 1-hexene.In embodiment, the polydispersity index of polymkeric substance is greater than approximately 15, and short-chain branched distribution maximum value is present between about 30kDa and the weight-average molecular weight of 1000kDa.In embodiment, the short-chain branched horizontal extent of polymkeric substance is for often amounting to approximately 0.1 to approximately 20 short chain branch of 1000 carbon atoms, and alternatively approximately 0.5 to approximately 15, or alternatively approximately 1 to approximately 10.

Openly the feature of the polymkeric substance of type can be the short-chain branched distribution of describing by Pearson VII Amp fitting of a curve herein, is wherein less than the peaked short-chain branched distribution slope value of the short-chain branched distribution in approximately maximum log weight-average molecular weight place in log weight-average molecular weight and is less than approximately-0.005.Pearson Amp fitting of a curve is based on Pearson VII model, and it comprises four adjustable parameter a, p, q and v0, corresponds respectively to amplitude, live width, shape-dependent constant He Dai center.Along with q → 1, band is reduced to Lorentz and distributes, and along with q approaches 50, obtains Gaussian distribution more or less.Therefore, for belt shape, the approximate Lorentz-Gauss model that mixes of Pearson VII curve fitting procedure.

Openly the polymkeric substance of type can be applied technology known in the art and forms and manufacture article or end-use goods herein, as extrude, blow molding, injection moulding, fiber sprinning, thermoforming and casting.The polymkeric substance that discloses type herein can present the workability of raising.

In embodiment, polymkeric substance comprises PE, and it can manufacture pipe by extruding.Extrude the method that means to prepare polymer pipe, comprise polymkeric substance or the multipolymer of extruding molten state by mould, thus cooling and formation polymer pipe.Hereinafter, the disclosure will relate to PE pipe, although other polymer product is also taken into account.

Pipe is extruded, in brief, and by carrying out as follows: by the effect conveying solid substance polymer pellets of rotary screw, then compress and melting pill by using of heat and shearing force; Then by homogeneous polymers melt Conveying to mould, to form the profile of final expectation.About the manufacture of pipe, then the extrudate (exiting the melt of mould) with annular shape forms, and cooling by a series of vacuum and water cooling tank.In pipe extrusion, there is multiple feed.Polymkeric substance feed can be the polyvinyl resin of precolor, or it can be the mixture (being called as " salt and pepper blend ") of natural polyethylene and color enriched material.In North America, the most common feed that pipe is extruded is " salt and pepper blend ".In other region European and in the world, the most common feed that pipe is extruded is the polyvinyl resin of precolor.Feed is strictly controlled, to obtain suitable finished product (pipe) and ultimate consumer's specification.In " salt and pepper blend " embodiment, color enriched material is that load has the nearly polyethylene support resin of the carbon black pellet of 40 weight percents; This enriched material is introduced into, to keep the carbon black concentration of final Guan Zhongyue 2.5 weight percents.

Then feed is supplied in extruder.Single Screw Extrusion device for the most common extruder system of managing production.The object of extruder is melting, homogenizes and carry polyethylene pill.Extrusion temperature general range is 170 DEG C to 260 DEG C, and this depends on extruder screw design and poly flowing property.

Then the polymkeric substance of melting passes through ring mould, so that melt is formalized.Then the molten polymer of ring form is pushed conventionally through setting or shaping tank, utilizes water to spray from exterior cooling simultaneously.Although pipe diameter directly determines by mould and calibration sleeve cylinder size, thickness of pipe depends on die clearance and the applied speed (draw-downspeed) that pulls.

Then, the pipe of desired size is cooling and curing.Cooling by the some water pots realizations of application, its middle external tube is immersed in water or water is sprayed onto pipe outside.Pipe is from the inside surface cool of outside surface.Inside pipe wall and internal surface may keep awfully hot for a long time, because polyethylene is poor conductor of heat.Finally, pipe is printed, and coils or cut into certain length.

In embodiment, PE pipe of the present disclosure presents the mechanical properties of enhancing, as anti-slow crack growth, natural draw ratio (NDR) increase, anti-Rapid Crack and be enough to ensure the intensity of regulation PE100.Specification PE100 means pressure rating, wherein essential intensity level (the 50 years estimated values at 20 DEG C of the minimum of pipe; 97.5 expection lower limits) be equal to or greater than 10.0MPa.This pipe can present the character of below describing alone or in combination.The concrete grammar of measuring these character has more detailed description in this article.

Most of field failures of penstock application are because slow crack growth (SCG).This has caused the exploitation of kinds of experiments chamber scale test, as Pennsylvania Edge-Notch Elongation test (PENT; ASTM F1473), to predict different poly anti-SCG.In PENT test, make to be with the creep of recess polyethylene sample experience by apply constant tensile loading at 80 DEG C.It is 3.8MPa that the load applying makes initial stress.Out-of-service time is recorded and reports.The longer out-of-service time is associated with larger anti-SCG.In general, increasing resin density reduces the PENT out-of-service time.Openly the PE pipe of type can present the PENT out-of-service time and be greater than approximately 800 hours (h) to approximately 2000 hours herein, is greater than alternatively about 1500h, or is greater than alternatively about 2000h.

Because the most of field failures in penstock (gas transport) application are because brittle rupture mode---be called as SCG, the anti-SCG of penstock is to being conventionally evaluated.A kind of method of evaluating anti-SCG is the natural draw ratio (stretching NDR) by determining resin.There is the directly related higher evidence of the lower anti-SCG of NDR that makes to stretch of anti-SCG of some stretching NDR and HDPE.SCG is found in the associated description of stretching NDR: E.Laurent, Comprehensive Evaluation of the Long-Term Mechanical Properties of PE100Resin Meeting the Requirements of Modern Installation Techniques, Plastic Pipes XIProceedings of the International Conference, Woodhead Publishing Limited (2001); With L.Hubert etc. 2002 in Journal of Applied Polymer Science Volume84, the 2308th page of article of delivering, wherein each is all incorporated to herein by reference.

By according to ASTM D638, dog bone (dogbone) sample being carried out to the experiment of standard tensile stress-strain with rate of deformation 51mm/min, measure stretching NDR.With reference to figure 1, show representative stress-strain curve, wherein tension strain is plotted as percent strain, and stress is represented as power or load (representing with 1bf).Flex point 20,40,50 and 60 monumented point place material behaviors change.At first, under low strained condition, observe linear section 10.In this linear section 10, material stands the stress (F) being directly proportional to applied strain (u), and material behavior can be estimated by Hook's law (equation 5), and wherein rate constant is elasticity or Young's modulus, represents with Y:

F=Yu (5)

And in linear section 10, deformational behavior is approximate elastic, that is, in the time removing the load applying, material strain returns to zero.The stress that fades to the point of plasticity from elasticity at material behavior is called as yielding stress.Apply the load that exceedes yield-point 20 and cause permanent (or plasticity) material deformation.Generally, poly yield-point 20 is significantly, is the maximum value of load-strain track shown in Fig. 1.Exceed yield-point, along with sample is continued to extend, the material outside dog bone sample neck region is pulled in neck; Load does not change a lot in this constriction and drawing process.This constriction/drawing process continues, until sample meets with the point 50 in " strain-sclerosis " or Fig. 1.Any further distortion that the generation of strain-sclerosis means sample in brief needs considerable energy input.This load in Fig. 1 is fairly obvious in significantly and sharply increasing.In other words, in the period that indicates 90 of strain hardening 50, now realizing given strain need to be than the larger stress of curve district finding before this.Percent strain when strain-sclerosis occurs is defined as the NDR that stretches.Load will finally cause material in rupture stress and strain point 60 places fracture to being continuously applied of material.

Some polymkeric substance do not present the obvious strain-sclerosis behavior shown in Fig. 1.Therefore,, for limiting stretching NDR, first need to meet following standard: the tensile stress of rent is than stretching yield stress height at least 10% (σ _brk>1.10* σ _y).

In embodiment, for example, be approximately 540% to approximately 600% by the stretching NDR scope of the goods (, pipe) that openly prepared by the polymkeric substance of type herein, be less than alternatively approximately 600%, be less than alternatively approximately 550%, or be less than approximately 540%.

Can be comprised the SCBD of some users and/or process expectation herein by the polymkeric substance that openly prepared by the CATCOMP of type.Can pass through the SCBD of the composition telomerized polymer that regulates CATCOMP, thereby provide target can be positioned at the SCBD of one or more restriction molecular weight ranges of polymer composition.

Embodiment

The disclosure is by the further example of the following example, and this embodiment is interpreted as its scope to impose restriction never in any form.On the contrary, will be clear that understanding, can adopt multiple other side, embodiment, change and equivalents thereof, it is being read after description herein and can imply that they are own to those skilled in the art, and does not depart from the scope of spirit of the present invention or claims.

The data that the following example provides and description are presented to show concrete aspect and the embodiment of open theme, and to prove multiple practice and advantage thereof.Example is presented the proof more in detail as aspects more described herein and embodiment, and is not intended to limit by any way the disclosure or claim.

Openly the CATCOMP of type is used for vinyl polymerization herein.Particularly, CATCOMP---comprise two (phenol) compounds of imines, in table 1, be named as structure XV; Metallocenic compound with structure 15 or structure 18---for the production of nine kinds of polyethylene specimen, called after sample S1-S9.Each sample is prepared by the mixture that comprises 1g S-SSA, 0.6ml TIBA and selected amount 1-hexene, makes this mixture stand the vinyl monomer of 450psi, and makes its polymerization 45min at 100 DEG C.

The different properties of polymer samples is also shown in table 1.The polymerization in the case of two (phenol) compounds of imines that represented by structure XV exist of comparative sample, is named as C1.Digital proof in table 1, by regulating catalyzer composition and reactor condition, produces and has polymer samples of different nature.The scope that catalyst combination, 1-hexene amount and hydrogen allow to enter HLMI.Generally, for allowing to enter the given combination of HLMI scope, the HLMI of polymer samples increases with hydrogen supply.And generally, the increase that the density of polymer samples adds with 1-hexene reduces.The GPC curve display of sample S3 and S9 is in Fig. 1.Comprise the compound being represented by structure 18 and 15 respectively as metallocene components for the preparation of the CATCOMP of sample S3 and S9.Obviously, sample S3 presents wider MWD, comprises lower M _p, and obvious HMW tail.Investigate herein the openly rheology of the polymkeric substance of type by monitoring as the dynamic fusion viscosity of the function of frequency.These results of sample S3 and S9 are presented in Fig. 2.These results with utilize the luxuriant system of bimetal, sample C2; Or chrome catalysts, polymkeric substance prepared by sample C3 compares.Polymkeric substance high shear of the present disclosure causes rare, is similar to chromium sample C3, and this shows that described material presents relevant workability while comparing to chromium system, presents workability with compared with the system of utilizing bimetal cyclopentadienyl catalyst to prepare time to significantly improve.Chromium sample C3 is the commercial reference resin of melt strength, and in view of with the rheology similarity of S3 and S9, should mean polymkeric substance of the present disclosure and should present suitable melt strength.

Measure herein the openly SCBD of the polymkeric substance---sample S3 and S10 particularly---of type by GPC, result is presented at respectively in Figure 4 and 5.Result shows, butyl branch is arranged in B component.Measure the stretching NDR of the different polymer samples that disclose type herein and be presented in table 2.As shown in table 2, comprise short chain branch and cause NDR (%) significantly to reduce and anti-slow crack growth increases by comprising the compound being represented by structure 15 and 18.For example, C1 is prepared in the non-existent situation of compound being represented by structure 15 or 18, and its NDR is 747.In polymerization, comprise density and NDR that the compound being represented by structure 15 or 18 reduces polymkeric substance.

The comparison that table 3 comprises the polymkeric substance (, utilizing CATCOMPS to prepare) with the polymkeric substance of preparing with chrome catalysts C3 and C4 that disclose type herein.Data presentation, for similar density, openly the anti-SCG of for example S2 of polymkeric substance of type and S12 improves herein, as NDR reduces given.

The anti-SCG raising measuring by NDR is proved by the PENT test in table 4.Under equal densities, the PENT of S5 is far better than C3.

Table 2

Sample number into spectrum	Density (g/cc)	NDR(％)
			C1	0.966	747.0
S1	0.950	543.8
			S2	0.952	537.2
S3	0.953	531.8

Sample number into spectrum	Density (g/cc)	NDR(％)
			S4	0.955	517.4
S5	0.948	504.0
			S6	0.953	580.7
S7	0.950	511.8
			S8	0.951	558.7
S9	0.949	518.5
			S10	0.946	464.5
S11	0.945	479.7
			S12	0.941	447.7

Table 3

Sample number into spectrum	Density (g/cc)	NDR(％)
			C3	0.947	591
S5	0.948	504
			C4	0.938	507
S12	0.941	448

Table 4

Result proves, the HMW end that SCB is placed in to wide distribution provides the fabulous polymkeric substance of anti-SCG, as indicated in NDR and PENT value.Comonomer is mixed with the polymkeric substance that utilizes CATCOMP of the present disclosure to prepare and presents character improvement, as the low NDR value across density range.

Provide the following embodiment of enumerating as limiting examples.

The first embodiment, it is polymer reactor adulterant, at least comprises the first component, the polydispersity index of described the first component be greater than approximately 20 and amount for based on the about 1wt.% of total polymer weight to about 99wt.%; And second component, the polydispersity index of described second component be less than approximately 20 and amount for based on the about 1wt.% of total polymer weight to about 99wt.%, wherein in the molecular weight distribution of the molecular weight distribution of second component in the first component.

The second embodiment, it is the polymkeric substance of the first embodiment, comprises the branching that is greater than approximately 75% in second component.

The 3rd embodiment, it is the polymkeric substance of the first or second embodiment, is formed by ethene and comonomer.

The 4th embodiment, it is the polymkeric substance of any one in the first to the 3rd embodiment, wherein the density of the first component is greater than about 0.950g/cc.

The 5th embodiment, it is the polymkeric substance of any one in the second to the 4th embodiment, wherein branching can be short-chain branched, long chain branching or the two.

The 6th embodiment, it is the polymkeric substance of any one in the 3rd to the 5th embodiment, wherein comonomer comprises 1-butylene, 1-hexene, 1-octene or its combination.

The 7th embodiment, it is the polymkeric substance of any one in the second to the 6th embodiment, wherein branching comprises short-chain branched.

The 8th embodiment, it is the polymkeric substance of the 7th embodiment, is wherein short-chain branchedly greater than every 1000 about 0.1SCB of carbon.

The 9th embodiment, it is the polymkeric substance of any one in aforementioned embodiments, its weight-average molecular weight is that about 50kg/mol is to about 1000kg/mol.

The tenth embodiment, it is the polymkeric substance of any one in aforementioned embodiments, its molecular weight distribution is approximately 4 to approximately 200.

The 11 embodiment, it is the polymkeric substance of any one in aforementioned embodiments, its CY-a value is approximately 0.05 to approximately 0.8.

The 12 embodiment, it is the polymkeric substance of any one in aforementioned embodiments, its short-chain branched content is that every 1000 carbon approximately 1 are to about 20SCB.

The 13 embodiment, it is the polymkeric substance of any one in aforementioned embodiments, its stretch ratio is less than approximately 600%.

The 14 embodiment, it is the polymkeric substance of any one in aforementioned embodiments, its PENT out-of-service time is greater than 800h, utilizes 3.8MPa stress determination according to ASTM F1473.

The 15 embodiment, it is the method for preparing polymer pipe, comprise: obtain polymkeric substance, described polymkeric substance is by contacting vinyl monomer to prepare with catalyst composition with 1-hexene under the condition being suitable for forming polymkeric substance, described catalyst composition comprises (i) imines (two) phenates compound, has structure XIV

Wherein M is the 3rd family's to the 12 group 4 transition metals or lanthanon,

R ²and R ³can be hydrogen, halogen, alkyl or substituted hydrocarbon radical independently of one another; (ii) metallocene, and Et ₂o is optional; With

Polymkeric substance is made to pipe, and wherein the zero-shear viscosity of polymkeric substance is extremely about 1E+10Pa-s of about 1E+05Pa-s, and natural draw ratio is less than approximately 600%, and wherein the PENT value of pipe is greater than approximately 800 hours, as utilized 3.8MPa stress determination according to ASTM F1473.

The 16 embodiment, it is polymer reactor adulterant, its polydispersity index be greater than approximately 15 and short-chain branched distribution maximum value appear between about 30kDa and the weight-average molecular weight of 1000kDa.

The 17 embodiment, it is the polymkeric substance of the 16 embodiment, the scope of its short-chain branched level is for often amounting to approximately 0.1 to approximately 20 short chain branch of 1000 carbon atoms, described by Pearson VII Amp fitting of a curve with short-chain branched distribution, be wherein less than approximately-0.005 in the peaked short-chain branched distribution slope value of the short-chain branched distribution in log weight-average molecular weight place that is less than approximately maximum log weight-average molecular weight.

The 18 embodiment, it is the 16 or the polymkeric substance of the 17 embodiment, it comprises polyethylene.

The 19 embodiment, it is the 16, the 17 or the polymkeric substance of the 18 embodiment, its utilization comprises the catalyst composition preparation of at least one imines (two) phenates compound, at least one Metallocenic compound and metal alkyl.

The 20 embodiment, it is by the 16, the 17, the 18 or the goods prepared of the polymkeric substance of the 19 embodiment.

Although embodiment of the present disclosure is shown and description, those skilled in the art can change it, and do not deviate from spirit of the present disclosure and instruction.Embodiment described herein is only exemplary, does not mean restricted.Multiple amendment and the change of disclosure are possible herein, and in the scope of the present disclosure.In the situation that numerical range or boundary are clearly explained, this clear and definite scope or boundary should be understood to include overlapping range or fall into similar magnitude boundary in described clear and definite scope or boundary that (for example, approximately 1 to approximately 10 comprises 2,3,4 etc.; Be greater than 0.10 and comprise 0.11,0.12,0.13 etc.).For example, in the time openly having the numerical range of lower limit R1 and upper limit Ru, any numerical value falling in scope is all disclosed particularly.Particularly, lower column of figure in scope is by specifically open: R=Rl+k* (Ru-Rl), wherein k is the variable with the scope from 1% to 100% of 1% increment,, k be 1%, 2%, 3%, 4%, 5% ..., 50%, 51%, 52% ..., 95%, 96%, 97%, 98%, 99% or 100%.In addition, if the Any Digit scope of two the R numerals restriction above limiting is also by open particularly.Use term " optionally " to mean for any key element of claim and need or do not need alternatively subject element.Two kinds of selections are all within the scope of claim.The use of more wide in range term, as comprise, comprise, have etc., should be understood to provide the support to narrower term, as by ... composition, mainly by ... composition, substantially by ... composition etc.

Therefore, the description that protection domain is not above made is limit, and is only subject to the restriction of claims, and its scope comprises all equivalents of claim theme.Each and each claim is all merged in specification sheets, as embodiment of the present disclosure.Therefore, claim is further describing of disclosure embodiment and supplements in addition.The discussion of reference herein is not to recognize that it is any reference that prior art of the present disclosure, particularly publication date may be after the application's right of priority dates.The disclosure of all patents, patent application and the publication of quoting is herein incorporated to herein by reference, make they for as herein described those provide in exemplary, program or other details supplement.

Claims

1. polymer reactor adulterant, it at least comprises the first component, the polydispersity index of described the first component be greater than approximately 20 and amount for based on the about 1wt.% of total polymer weight to about 99wt.%; And second component, the polydispersity index of described second component be less than approximately 20 and amount for based on the about 1wt.% of total polymer weight to about 99wt.%, in the molecular weight distribution of the molecular weight distribution of wherein said second component in described the first component.

2. polymkeric substance claimed in claim 1, comprises the branching that is greater than approximately 75% in described second component.

3. polymkeric substance claimed in claim 2, it is formed by ethene and comonomer.

4. polymkeric substance claimed in claim 2, the density of wherein said the first component is greater than about 0.950g/cc.

5. polymkeric substance claimed in claim 3, wherein said branching can be short-chain branched, long chain branching or the two.

6. polymkeric substance claimed in claim 3, wherein said comonomer comprises 1-butylene, 1-hexene, 1-octene or its combination.

7. polymkeric substance claimed in claim 2, wherein said branching comprises short-chain branched.

8. polymkeric substance claimed in claim 7, wherein said short-chain branched every 1000 about 0.1SCB of carbon that are greater than.

9. polymkeric substance claimed in claim 1, its weight-average molecular weight is that about 50kg/mol is to about 1000kg/mol.

10. polymkeric substance claimed in claim 1, its molecular weight distribution is approximately 4 to approximately 200.

11. polymkeric substance claimed in claim 1, its CY-a value is approximately 0.05 to approximately 0.8.

Polymkeric substance described in 12. claims 11, its short-chain branched content is that every 1000 carbon approximately 1 are to about 20SCB.

13. polymkeric substance claimed in claim 8, its stretch ratio is less than approximately 600%.

14. polymkeric substance claimed in claim 8, its PENT out-of-service time is greater than 800h, as utilized 3.8MPa stress to be measured according to ASTM F1473.

15. prepare the method for polymer pipe, comprising:

Obtain polymkeric substance, described polymkeric substance by under the condition being suitable for forming polymkeric substance by vinyl monomer and 1-hexene and catalyst composition contact preparation, described catalyst composition comprises (i) imines (two) phenates compound, has structure XIV

Wherein M is the 3rd family's to the 12 group 4 transition metals or lanthanon,

Polymkeric substance is made to pipe, to be about 1E+05Pa-s be less than approximately 600% to about 1E+10Pa-s and natural draw ratio to the zero-shear viscosity of wherein said polymkeric substance, and the PENT value of wherein said pipe is greater than approximately 800 hours, as utilized 3.8MPa stress to be measured according to ASTM F1473.

16. polymer reactor adulterants, its polydispersity index be greater than approximately 15 and short-chain branched distribution maximum value appear between about 30kDa and the weight-average molecular weight of 1000kDa.

Polymkeric substance described in 17. claims 16, the scope of its short-chain branched level is described by Pearson VII Amp fitting of a curve for often amounting to approximately 0.1 to approximately 20 short chain branch of 1000 carbon atoms and short-chain branched distribution, is wherein less than approximately maximum log weight-average molecular weight place in log weight-average molecular weight and states the peaked short-chain branched distribution slope value of short-chain branched distribution and be less than approximately-0.005.

Polymkeric substance described in 18. claims 16, it comprises polyethylene.

Polymkeric substance described in 19. claims 16, it utilizes catalyst composition preparation, and described catalyst composition comprises at least one imines (two) phenates compound, at least one Metallocenic compound and metal alkyl.

20. goods, are prepared by the polymkeric substance described in claim 16.